Polymeric stabilizers having low polydispersity

ABSTRACT

The present invention relates to a polymerizable composition, comprising a) at least one compound of formula (I) 
     
       
         (RG)—A—(Stab)  (I), 
       
     
     wherein 
     (Stab) is a light stabilizer radical selected from the group consisting of sterically hindered amines, hydroxyphenyl-s-triazines, hydroxyphenyl-benzotriazols and o-hydroxy-benzophenones; A is a spacer group or a direct bond; and 
     (RG) is a group containing at least one ethylenically unsaturated functional group; and either b1) a compound of formula (II) 
     
       
         Y—X  (II), 
       
     
      wherein 
     X represents a group having at least one carbon atom and is such that the free radical derived from X is capable of initiating polymerization and 
     Y represents a group being such that the free radical Y· derived from it forms a stable free radical; or b2) a stable free radical Y· and a free radical source from which a radical is formed capable of initiating polymerization, or b3) a compound of formula (III)                    
      and a catalytically effective amount of an oxidizable transition metal complex catalyst, wherein 
     p represents a number greater than zero and defines the number of initiator fragments; 
     q represents a number greater than zero; 
     [In] represents a radically transferable atom or group capable of initiating polymerization and -[Hal] represents a leaving group; and optionally c) one or more ethylenically unsaturated monomers or oligomers different from those of formula (I). Further subjects of the invention are a polymerization process, the polymers, copolymers oligomers and cooligomers obtainable by this process and the use of the polymers, copolymers oligomers and cooligomers as heat or light stabilizers.

The present invention relates to radically polymerizable compositions,containing at least one light stabilizer with an ethylenicallyunsaturated group and to oligomers, polymers, cooligomers or copolymershaving low polydispersity M_(w)/M_(n), which are prepared by controlledradical polymerization from the polymerizable composition. Furtheraspects of the invention are a process for their preparation, their useas light or heat stabilizers for organic materials, particularly forsynthetic polymers, paints, enamels or varnishes and the organicmaterials thus stabilized.

The stabilization of polymers with light/heat stabilizers such as2,2,6,6-tetramethylpiperidine derivatives, hydroxy-benzophenones,hydroxy-benzotriazoles and hydroxy-phenyl-s-triazines is well known. Itis also known to prepare and to use oligomeric or polymeric lightstabilizers of the above mentioned classes for the stabilization ofpolymers. This is for example described in U.S. Pat. No. 4,294,949 andin U.S. Pat. No. 4,785,063. These polymeric light stabilizers are allprepared by a conventional free radical polymerization process.

However polymers or copolymers prepared by free radical polymerizationprocesses inherently have broad molecular weight distributions orpolydispersities which are generally higher than about four. One reasonfor this is that most of the free radical initiators have half livesthat are relatively long, ranging from several minutes to many hours,and thus the polymeric chains are not all initiated at the same time andthe initiators provide growing chains of various lengths at any timeduring the polymerization process.

Due to the broad molecular weight distribution and high molecularweights of the polymeric light stabilizers problems arise when they areincorporated into paints, coatings, or thermoplastic polymers. Theycause for example a strong viscosity increase in paints and coatings,which is undesirable for the paint's application, in particular for thespray application of automotive coatings. In thermoplastic polymerscompatibility problems may arise particularly with the high molecularweight portion of the polymeric light stabilizers. For these reasonspolymeric light stabilizers having a low polydispersity are desirablefor many applications.

The light stabilizers of the present invention are polymeric resinproducts having low polydispersity. The polymerization process proceedswith good monomer to polymer conversion efficiency, thus being alsofeasible on an industrial scale. In particular, this invention relatesto stable free radical-mediated polymerization processes or to a, freeradical initiated polymerization process by the ATRP (Atom TransferRadical Polymerization) method which provide homopolymers, alternate-,gradient- or random copolymers, block copolymers or multiblockcopolymers of different classes of light stabilizers.

The so made polymers or copolymers are highly compatible withthermoplastic polymers and thermosetting coatings. They are veryefficient light/heat stabilizers either when used alone or incombination with other known stabilizers. Due to their lowpolydispersity they are easy to incorporate into other polymers, withoutfor example significantly increasing their viscosity or meltingproperties.

One subject of the present invention is a polymerizable composition,comprising a) at least one compound of formula (I)

(RG)—A—(Stab)  (I),

wherein

(Stab) is a light stabilizer radical selected from the group consistingof sterically hindered amines, hydroxyphenyl-s-triazines,hydroxyphenyl-benzotriazols and o-hydroxy-benzophenones; A is a spacergroup or a direct bond; and

(RG) is a group containing at least one ethylenically unsaturatedfunctional group; and either b1) a compound of formula (II)

Y—X  (II),

 wherein

X represents a group having at least one carbon atom and is such thatthe free radical derived from X is capable of initiating polymerizationand

Y represents a group being such that the free radical Y· derived from itforms a stable free radical; or b2) a stable free radical Y· and a freeradical source from which a radical is formed capable of initiatingpolymerization; or b3) a compound of formula (III)

 and a catalytically effective amount of an oxidizable transition metalcomplex catalyst, wherein

p represents a number greater than zero and defines the number ofinitiator fragments;

q represents a number greater than zero;

[In] represents a radically transferable atom or group capable ofinitiating polymerization and -[Hal] represents a leaving group; andoptionally c) one or more ethylenically unsaturated monomers oroligomers different from those of formula (I).

The sterically hindered amines are preferably selected from the class ofpiperidines, piperazinones, piperazindiones or morpholinones.

Preferably component a) of formula (I) is a compound of formulae (Ia),(Ib), (Ic), (Id), (Ie), (If), (Ig), (Ih), (Ii) or (Ij)

W is O, or NR₁₁₀;

A is a direct bond, —(C₂-C₁₂)alkylene-W—, —(C₃-C₁₂)alkenylene-W—,—CH₂—HC(OH)—CH₂—W—, —(C₃-C₁₂)alkinylene-W—, (C₅-C₁₂)cycloalkylene-W—,—(C₂-C₁₂)alkylene-W— interrupted by at least one oxygen or nitrogen atomor a group —CH₂—CHR₁₁₀—W—, a group —CHR₁₁₁—COOP wherein P is—(CH₂—HCR₁₁₂)_(n)— or a group —CH₂—HC(OH)—CH₂—, wherein R₁₁₀, R₁₁₁, R₁₁₂and n are as defined below;

R₁₁₀ is H or methyl R₁₀₂ is hydrogen, OH, C₁-C₁₈alkyl, C₃-C₈alkenyl,C₃-C₈alkynyl; C₇-C₁₂aralkyl, C₁-C₁₈alkanoyl, C₃-C₁₈alkenoyl,C₁-C₁₈alkanoyloxy, glycidyl, C₁-C₁₈alkoxy, C₅-C₁₂cycloalkyl,C₅-C₁₂cycloalkoxy or a group —CH₂CHR₁₁₀(OH);

R₁₀₃ is H, OH, NH₂, C₁-C₁₈alkoxy, C₁-C₁₈alkanoyloxy, C₆-C₁₈aryloyloxy,C₁-C₁₈alkanoylamino, C₁-C₁₈alkylamino, C₁-C₁₈alkylamino, benzyloxy ortogether with the linking carbon atom forms a C₅-C₆cycloalkyl radical ora C₅-C₆heterocycloalkyl radical containing one or two oxygen or nitrogenatoms;

R₁₀₄, R₁₀₅, R₁₀₆, R₁₀₇ are independently C₁-C₈alkyl or C₅-C₁₂cyloalkyl,or R₁₀₄ and R₁₀₅ and/or R₁₀₆ and R₁₀₇ together with the carbon atom towhich they are attached form-a C₅-C₁₂cycloalkyl group;

R₁₀₈ and R₁₀₉ independently are H, C₁-C₈alkyl or phenyl;

R₁₁₀ is hydrogen, C₁-C₁₈alkyl or phenyl;

R₁₁₁ is hydrogen or C₁-C₁₂alkyl;

R₁₁₂ is hydrogen or methyl;

R₂₀₁ and R₂₀₂ are independently H, OH, CN, C₁-C₁₈alkyl, C₁-C₁₈alkoxy,halogen, C₁-C₁₈alkanoyl, C₁-C₁₈alkanoyloxy, C₁-C₁₈alkanoylamino, orphenyl which is unsubstituted or substituted with halogen, OH, CN, NO₂,C₁-C₁₈alkyl, C₁-C₁₈alkoxy or a group —O—CH₂—HC(OH)—CH₂—OR₂₀₆;

R₂₀₃ and R₂₀₄ are independently H, OH, CN, C₁-C₁₈alkyl, C₁-C₁₈alkoxy,halogen, C₁-C₁₈alkanoyl, C₁-C₁₈alkanoyloxy, C₁-C₁₈alkanoylamino, orphenyl which is unsubstituted or substituted with halogen, OH, CN, NO₂,C₁-C₁₈alkyl, C₁-C₁₈alkoxy or a group —O—CH₂—HC(OH)—CH₂—OR₂₀₆ with theproviso that at least one of both is OH;

R₂₀₅ is H, halogen, phenyl, C₁-C₁₈alkyl, C₅-C₁₂cycloalkyl, C₇-C₁₂aralkylor a group —SR₂₀₈, —SO₂R₂₀₈, —COOR₂₀₈ or PO(OR₂₀₈)₂;

R₂₀₆ is C₁-C₁₈alkyl, C₃-C₁₈alkyl interrupted by at least one oxygenatom, phenyl which is unsubstituted or substituted with halogen, OH, CN,NO₂, C₁-C₁₈alkyl, C₁-C₁₈alkoxy, C₅-C₆cycloalkyl which is unsubstitutedor substituted by C₁-C₄alkyl or a group —C(O)R₂₀₇;

R₂₀₇ C₁-C₁₈alkyl or phenyl which is unsubstituted or substituted withhalogen, OH, CN, NO₂, C₁-C₁₈alkyl or C₁-C₁₈alkoxy;

R₂₀₈ is C₁-C₁₈alkyl, C₅-C₆cycloalkyl or phenyl;

R₂₀₉ is H, halogen, phenyl, C₁-C₁₈alkyl, C₅-C₁₂cycloalkyl, C₇-C₁₂aralkylor a group —SR₂₀₈, —SO₂R₂₀₈, —COOR₂₀₈ or PO(OR₂₀₈)₂;

n is a number from 0 to 12, and

k is a number from 0 to 12.

Preferably R₁₀₈ and R₁₀₉ are hydrogen and the other substituents are asdefined above.

Preferably R₁₀₄, R₁₀₅, R₁₀₆ and R₁₀₇ are methyl and the othersubstituents are as defined above.

Preferably A is a direct bond, —(C₂-C₆)alkylene-W—, —(C₂-C₁₂)alkylene-W—interrupted by at least one oxygen or nitrogen atom or a group—CH₂—CHCH₃—W—.

W is preferably an oxygen atom.

R₁₀₂ is preferably hydrogen, C₁-C₈alkyl, allyl, benzyl, C₁-C₈alkanoy),C₁-C₈alkanoyloxy, C₁-C₈alkoxy or cyclohexyloxy.

Preferably R₁₀₃ is H, C₁-C₈alkoxy, C₁-C₈alkanoyloxy, benzyloxy,C₁-C₈alkylamino, C₁-C₈dialkylamino or C₁-C₈alkanoylamino.

R₂₀₁, R₂₀₂, R₂₀₃ and R₂₀₄ are independently H, C₁-C₈alkyl, OH,C₁-C₈alkoxy, phenyl or halogen, with the proviso that at least one ofR₂₀₃ or R₂₀₄ is OH.

Preferably R₂₀₅ is hydrogen, halogen or C₁-C₈alkyl.

Preferably R₂₀₆ is C₁-C₄alkyl or phenyl.

R₂₀₇ is preferably C₁-C₄alkyl or phenyl which is unsubstituted orsubstituted with C₁-C₁₈alkoxy;

R₂₀₈ is pereferably C₁-C₄alkyl or phenyl;

Preferably n is a number from 2-6 and k is a number from 0-2.

Preferably the compound of formula (I) is a compound of formulae (Ia),(Ic), (Id), (If), (Ig), (Ii) or I(j), more preferably of formulae (Ia),(If), (Ig) or (Ii).

Preferred is a composition, wherein in the compound of formula (Ia), Ais a direct bond, C₂-C₆alkylene or C₂-C₆alkylene interrupted by at leastone oxygen or nitrogen atom; RG is a group

W is an oxygen atom;

R₁₀₁ is H or methyl

R₁₀₂ is H, C₁-C₄alkyl, allyl, benzyl, C₁-C₆alkoxy, cyclohexyloxy, acetylor acryloyl;

R₁₀₄-R₁₀₇ are methyl and

R₁₀₈ and R₁₀₉ are hydrogen.

Particularly preferred is a composition, wherein in the compound offormula (Ia), A is a direct bond; W is an oxygen atom; RG is a group

R₁₀₁ is H or methyl; R₁₀₂ is H or C₁-C₄alkyl; R₁₀₄-R₁₀₇ are methyl; andR₁₀₈ and R₁₀₉ are hydrogen.

Also preferred is a composition, wherein in the compounds of formulae(If), (Ig) or (Ii)

A is a direct bond, C₂-C₆alkylene or C₂-C₆alkylene interrupted by atleast one oxygen or nitrogen atom

W is an oxygen atom;

RG is a group

R₁₀₁ is H or methyl;

R₂₀₁ and R₂₀₂ are independently H, C₁-C₈alkyl, phenyl or OH;

R₂₀₃ and R₂₀₄ are independently H, C₁-C₈alkyl, phenyl or OH with theproviso that at least one of both is OH;

R₂₀₅ is H, C₁-C₈alkyl or α-cumyl;

R₂₀₉ is H or Cl;

and k is a number from 1 to 8.

Particularly preferred is a composition, wherein in the compound offormula (Ii)

A is a direct bond

W is an oxygen atom;

RG is a group

R₁₀₁ is H or methyl;

R₂₀₅ is H C₁-C₈alkyl, phenyl or α-cumyl;

R₂₀₉ is H or Cl and

k is a number from 1 to 8.

The alkyl radicals in the various substituents may be linear orbranched. Examples of alkyl containing 1 to 18 carbon atoms are methyl,ethyl, propyl, isopropyl, butyl, 2-butyl, isobutyl, t-butyl, pentyl,2-pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, t-octyl, nonyl, decyl,undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl and octadecyl.

Alkenyl with 3 to 18 carbon atoms is a linear or branched radical as forexample propenyl, 2-butenyl, 3-butenyl, isobutenyl, n-2,4-pentadienyl,3-methyl-2-butenyl, n-2-octenyl, n-2-dodecenyl, iso-dodecenyl, oleyl,n-2-octadecenyl oder n-4-octadecenyl.

Preferred is alkenyl with 3 bis 12, particularly preferred with 3 to 8carbon atoms. C₃-C₈alkenyl can be, for example, 1-propenyl, allyl,methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl, 2-octenyl, or4-tert-butyl-2-butenyl.

Alkinyl with 3 to 18 is a linear or branched radical as for examplepropinyl (—CH₂—C≡CH), 2-butinyl, 3-butinyl, n-2-octinyl, odern-2-octadecinyl. Preferred is alkinyl with 3 to 12, particularlypreferred with 3 to 8 carbon atoms. C₃-C₈alkynyl is most preferablypropargyl.

Examples of C₅-C₁₂cycloalkyl are cyclopentyl, cyclohexyl, cycloheptyl orcyclooctyl. Preferred are cycloheptyl and cyclohexyl.

Examples of alkylene containing 1 to 18 carbon atoms are methylene,ethylene, propylene, isopropylene, butylene, 2-butylene, isobutylene,t-butylene, pentylene, 2-pentylene, hexylene, heptylene, octylene,2-ethylhexylene, t-octylene, nonylene, decylene, undecylene, dodecylene,tridecylene, tetradecylene, hexadecylene and octadecylene.

C₂-C₁₈alkylene interrupted by at least one O atom is for example—CH₂—CH₂—O—CH₂—CH₂—, —CH₂—CH₂—O—CH₂— or—CH₂—CH₂—O—CH₂—CH₂—CH₂—O—CH₂—CH₂—. It is preferably derived frompolyethlene glycol. A general description is —((CH₂)_(a)—O)_(b)—/CH₂—,wherein a is a number from 1 to 6 and b is a number from 2 to 10.

Alkenylene with 3 to 18 carbon atoms is a linear or branched radical asfor example propenylene, 2-butenylene, 3-butenylene, isobutenylene,n-2,4-pentadienylene, 3-methyl-2-butenylene, n-2-octenylene,n-2-dodecenylene, iso-dodecenylene, n-2-octadecenylene orn-4-octadecenylene.

Alkinylene with 3 to 18 is a linear or branched radical as for examplepropinylene, 2-butinylene, 3-butinylene, n-2-octinylene, orn-2-octadecinylene. C₇-C₉phenylalkyl is benzyl, phenylethyl orphenylpropyl, especially benzyl.

C₁-C₈alkanoyl is, for example, formyl, propionyl, butyryl, octanoyl, butpreferably acetyl and C₃-C₅alkenoyl is in particular acryloyl.

C₁-C₁₈alkanoyloxy is, for example, formyloxy, acetyloxy, propionyloxy,butyryloxy, valeryloxy, lauroyloxy, palmitoyloxy and stearoyloxy.

C₅-C₇cycloalkylene is typically, cyclopentylene, methylcyclopentylene,dimethylcyclopentylene, cyclohexylene, methylcyclohexylene orcyclopentylene.

Halogen is Fluorine, Chlorine, Bromine or Iodine, preferably Chlorine orBromine.

In the compounds according to formula (Ib) R₁₀₃ may form together withthe linking carbon atom a C₅-C₆cycloalkyl radical or aC₅-C₆heterocycloalkyl radical containing one or two oxygen or nitrogenatoms. Typical examples are derived from

50) 9-aza-8,8,10,10-tetramethyl-1,5-dioxaspiro[5.5]undecane

51) 9-aza-8,8,10,10-tetramethyl-3-ethyl-1,5-dioxaspiro[5.5]undecane

52) 8-aza-2,7,7,8,9,9-hexamethyl-1,4-dioxaspiro[4.5]decane

53)9-aza-3-hydroxymethyl-3-ethyl-8,8,9,10,10-pentamethyl-1,5-dioxaspiro[5.5]undecane

54)9-aza-3-ethyl-3-acetoxymethyl-9-acetyl-8,8,10,10-tetramethyl-1,5-dioxaspiro[5.5]undecane

55)2,2,6,6-tetramethylpiperidine-4-spiro-2′-(1′,3′-dioxane)-5′-spiro-5″-(1″,3″-dioxane-2″-spiro-4′″-(2′″,2′″,6′″,6′″-tetramethylpiperidine)or from

56) 3-benzyl-1,3,8-triaza-7,7,9,9-tetramethylspiro[4.5]decane-2,4-dione

57) 3-n-octyl-1,3,8-triaza-7,7,9,9-tetramethylspiro[4.5]decane-2,4-dione

58) 3-allyl-1,3,8-triaza-1,7,7,9,9-pentamethylspiro[4.5]decane-2,4-dione

59)3-glycidyl-1,3,8-triaza-7,7,8,9,9-pentamethylspiro[4.5]decane-2,4-dione

60) 1,3,7,7,8,9,9-heptamethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione

61)2-isopropyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decane

62)2,2-dibutyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decane

63)2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxodispiro[5.1.11.2]heneicosane

64) 2-butyl-7,7,9,9-tetramethyl-1-oxa-4,8-diaza-3-oxospiro[4.5]decaneand preferably:

65)8-acetyl-3-dodecyl-1,3,8-triaza-7,7,9,9-tetramethylspiro[4.5]decane-2,4-dione

The composition may contain additional ethylenically unsaturatedmonomers or oligomers as component c).

Preferably the ethylenically unsaturated monomer or oligomer is selectedfrom the group consisting of styrene, substituted styrene, conjugateddienes, acrolein, vinyl acetate, (alkyl)acrylic acid anhydrides,acrylonitrile, (alkyl)acrylic acid salts, (alkyl)acrylic esters or(alkyl)acrylamides.

More preferably the ethylenically unsaturated monomer is i-butylene,styrene, α-methyl styrene, p-methyl styrene or a compound of formulaCH₂═C(R_(a))—(C═Z)—R_(b), wherein R_(a) is hydrogen or C₁-C₄alkyl, R_(b)is NH₂, O⁻(Me⁺), glycidyl, unsubstituted C₁-C₁₈alkoxy, C₁-C₁₈alkoxyinterrupted by at least one N and/or O atom, or hydroxy-substitutedC₁-C₁₈alkoxy, C₁-C₁₈alkoxy interrupted by at least one N and/or O atom,unsubstituted C₁-C₁₈alkylamino, di(C₁-C₁₈alkyl)amino;hydroxy-substituted C₁-C₁₈alkylamino or hydroxy-substituteddi(C₁-C₁₈alkyl)amino, —O—CH₂—CH₂—N(CH₃)₂ or —O—CH₂—CH₂—N⁺H(CH₃)₂ An⁻;

An⁻ is a anion of a monovalent organic or inorganic acid;

Me is amonovalent metal atom, NH₄ ⁺ or HN⁺(C₁-C₄alkyl)₃; and

Z is oxygen or sulfur.

More preferably the ethylenically unsaturated monomer is styrene,α-methyl styrene, p-methyl styrene or a compound of formulaCH₂═C(R_(a))—(C═Z)R_(b), wherein R_(a), is hydrogen or C₁-C₄alkyl, R_(b)is NH₂, O⁻(Me⁺), glycidyl, unsubstituted C₁-C₁₈alkoxy orhydroxy-substituted C₁-C₁₈alkyloxy, unsubstituted C₁-C₁₈alkylamino,di(C₁-C₁₈alkyl)amino, hydroxy-substituted C₁-C₁₈alkylamino orhydroxy-substituted di(C₁-C₁₈alkyl)amino;

Me is a monovalent metal atom

Z is oxygen or sulfur.

Examples of monovalent metal atoms are Li, Na, K.

Examples of the anion An⁻ of a monovalent organic or inorganic acid areC₁-C₁₈carbonic acid anions, the anions of HClO₄, HCl or HBr.

Particularly preferred are monomers wherein R_(a) is hydrogen or methyl,R_(b) is NH₂, gycidyl, unsubstituted or with hydroxy substitutedC₁-C₄alkoxy, unsubstituted C₁-C₄alkylamino, di(C₁-C₄alkyl)amino,hydroxy-substituted C₁-C₄alkylamino or hydroxy-substituteddi(C₁-C₄alkyl)amino; and

Z is oxygen.

Most preferably the ethylenically unsaturated monomer is methylacrylate,ethylacrylate, butylacrylate, isobutylacrylate, tert. butylacrylate,hydroxyethylacrylate, hydroxypropylbutylacrylate,dimethylaminoethylacrylate, glycidylacrylates, methyl(meth)acrylate,ethyl(meth)acrylate, butyl(meth)acrylate, hydroxyethyl(meth)acrylate,hydroxypropyl(meth)acrylate, dimethylaminoethyl(meth)acrylate,glycidyl(meth)acrylates, acrylonitrile, acrylamide or methacrylamide.

Suitable compounds of formula (II)

Y—X  (II),

free radicals X· and stable free radicals Y· are known. Stable freeradicals having a structural element

are for example disclosed in EP-A-621 878.

Further examples such as

are given in WO 96/24620.

Another suitable stable free radical,1,3,5,5-Tetraphenyl-1,2,4-triazolin-2-yl, has been described by D.Colombani, M. Steenbock, M. Klapper, K. Müllen in Macromol. Rapid.Commun. 18, 243-251 (1997). Further suitable compounds and theirpreparation are given in WO 99/03894, GB 2 335 190 and in PCT/EP99/05377.

Initiator/regulator compounds of formula (II) containing a structuralelement

are in principal known. Suitable compounds and their manufacture are forexample described in U.S. Pat. No. 4,581,429, U.S. Pat. No. 5,721,320,U.S. Pat. No. 5,627,248, WO 98/13392, WO 98/30601 or in WO 98/44008.

The composition comprises preferably as component b1) a compound offormula (II)

Y—X  (II),

which contains a structural element

wherein the nitrogen atom is part of a cyclic ring system or issubstituted to form a acyclic structure.

A preferred acyclic structure is, wherein the compound containing astructural element

is of formula (XXa), (XXb) or (XXc)

wherein

Y₁ is O or CH₂;

Q₁ is O or NR₄₀, wherein R₄₀ is hydrogen or C₁-C₁₈alkyl;

R₂₁ is tertiary C₄-C₁₈alkyl or phenyl, which are unsubstituted orsubstituted by halogen, OH, COOR₄₁ or C(O)—R₄₂ wherein R₄₁ is hydrogen,a alkali metal atom or C₁-C₁₈alkyl and R₄₂ is C₁-C₁₈alkyl; or

R₂₁ is C₅-C₁₂cycloalkyl, C₅-C₁₂cycloalkyl which is interrupted by atleast one O or N atom, a polycyclic alkyl radical or a polycyclic alkylradical which is interrupted by at least one O or N atom;

R₂₂ and R₂₃ are independently C₁-C₁₈alkyl, benzyl, C₅-C₁₂cycloalkyl orphenyl, which are unsubstituted or substituted by halogen, OH, COOR₄₁ orC(O)—R₄₂ or together with the carbon atom form a C₅-C₁₂cycloalkyl ring;

if Y₁ is O, R₂₄ and R₃₂ are OH, O(alkali-metal) C₁-C₁₈alkoxy, benzyloxy,NR₄₃R₄₄, wherein R₄₃ and R₄₄ are independently from each other hydrogen,C₁-C₁₈alkyl or phenyl, which are unsubstituted or substituted byhalogen, OH, COOR₄₁ or C(O)—R₄₂;

if Y₁ is CH₂, R₂₄ is OH, C₁-C₁₈alkoxy, benzyloxy, O—C(O)—(C₁-C₁₈)alkylor NR₄₃R₄₄;

R₃₂ are a group C(O)R₄₅, wherein R₄₅ is OH, C₁-C₁₈alkoxy, benzyloxy,NR₄₃R₄₄, wherein R₄₃ and R₄₄ are independently from each other hydrogen,C₁-C₁₈alkyl or phenyl, which are unsubstituted or substituted byhalogen, OH, COOR₄₁ or C(O)—R₄₂;

R₂₅, R₂₆, R₂₇ and R₂₈ are independently of each other C₁-C₁₈alkyl,C₅-C₁₂cycloalykyl or phenyl; or

R₂₅ and R₂₆ and/or R₂₇ and R₂₈ together with the carbon atom form aC₅-C₁₂cycloalkyl ring;

R₂₉ and R₃₀ are independently of each other hydrogen,C₁-C₁₈alkylcarbonyl, benzoyl, C₁-C₁₈alkyl, C₅-C₁₂cycloalkyl,C₅-C₁₂cycloalkyl which is interrupted by at least one O or N atom,benzyl or phenyl which are unsubstituted or substituted by halogen, OH,COOR₄₁ or C(O)—R₄₂;

R₃₁, is C₁-C₁₈alkylcarbonyl, benzoyl, C₁-C₁₈alkyl, C₅-C₁₂cycloalkyl,C₅-C₁₂cycloalkyl which is interrupted by at least one O or N atom,benzyl or phenyl which are unsubstituted or substituted by halogen, OH,COOR₄₁ or C(O)—R₄₂; and

X represents a group having at least one carbon atom and is such thatthe free radical X· derived from X is capable of initiatingpolymerization of ethylenically unsaturated monomers.

Examples for the different substituents have been already given.

Typical examples of suitable compounds are given in Table 1. Thesecompounds and there preparation is described in PCT/EP 99/05377.

TABLE 1 No. Structure 201

202

203

204

205

206

207

208

209

210

211

212

213

214

Other suitable compounds with symmetrical substitution pattern arederived from nitroso compounds or nitrons and are described in WO99/03894. Typical examples are given in Table 2. The nitroso and nitronecompounds can also be used as in situ precursors to form the compoundsof Table 2 simultaneously to the polymerization step. This is describedin WO 99/03894.

TABLE 2 No. Compound 301

302

307

308

Preferably the initiator/regulator compounds form a cyclic structure

which may be a 5, 6, 7 or 8 ring system having no hydrogen atom inα-position to the nitrogen atom and which may contain one additionalheteroatom in the ring.

Particularly suitable initiator/regulator compounds are1-alkoxy-polyalkyl-piperidine derivatives containing a structuralelement of formula (X)

G₁, G₂, G₃, G₄ are independently C₁-C₆alkyl with the proviso that atleast one is not methyl or G₁ and G₂ or G₃ and G₄, or G₁ and G₂ and G₃and G₄ together form a C₅-C₁₂cycloalkyl group;

G₅, G₆ independently are H, C₁-C₁₈alkyl, phenyl, naphthyl or a groupCOOC₁-C₁₈alkyl and

X represents a group having at least one carbon atom and is such thatthe free radical X· derived from X is capable of initiatingpolymerization of ethylenically unsaturated monomers.

These compounds and their preparation are described in GB 2 335 190.

Particularly suitable compounds are listed in Table 3.

TABLE 3 No. Compound 401

402

403

404

405

406

407

408

409

410

411

412

Another preferred class of initiators are those of formula (Xa) or (Xb)

R₁, R₂, R₃ and R₄ independently of each other are C₁-C₁₈alkyl,C₃-C₁₈alkenyl, C₃-C₁₈alkinyl, C₁-C₁₈alkyl, C₃-C₁₈alkenyl, C₃-C₁₈alkinylwhich are substituted by OH, halogen or a group —O— C(O)—R₅, C₂-C₁₈alkylwhich is interrupted by at least one O atom and/or NR₅ group,C₃-C₁₂cycloalkyl or C₆-C₁₀aryl or R₁ and R₂ and/or R₃ and R₄ togetherwith the linking carbon atom form a C₃-C₁₂cycloalkyl radical;

R₅, R₆ and R₇ independently are hydrogen, C₁-C₁₈alkyl or C₆-C₁₀aryl;

X represents a group having at least one carbon atom and is such thatthe free radical X· derived from X is capable of initiatingpolymerization of ethylenically unsaturated monomers;

Z₁ is O or NR₈;

R₈ is hydrogen, OH, C₁-C₁₈alkyl, C₃-C₁₈alkenyl, C₃-C₁₈alkinyl,C₁-C₁₈alkyl, C₃-C₁₈alkenyl, C₃-C₁₈alkinyl which are substituted by oneor more OH, halogen or a group —O—C(O)—R₅, C₂-C₁₈alkyl which isinterrupted by at least one O atom and/or NR₅ group, C₃-C₁₂cycloalkyl orC₆-C₁₀aryl, C₇-C₉phenylalkyl, C₅-C₁₀heteroaryl, —C(O)—C₁-C₁₈alkyl,—O—C₁-C₁₈alkyl or —COOC₁-C₁₈alkyl;

Q is a direct bond or a divalent radical CR₉R₁₀, CR₉R₁₀—CR₁₁R₁₂,CR₉R₁₀CR₁₁R₁₂CR₁₃R₁₄, C(O) or CR₉R₁₀C(O), wherein R₉, R₁₀, R₁₁, R₁₂, R₁₃and R₁₄ are independently hydrogen, phenyl or C₁-C₁₈alkyl.

The compounds and their preparation are described in WO 98/30601, WO98/44008 and in the British patent application No. 9923579.8.

Particularly useful are the compounds listed in Table 4, 5 and 6.

TABLE 4 5-ring compounds No. Structure 101

102

105

106

TABLE 5 6-ring compounds No. Structure 107

108

109

110

111

112

113

114

115

116

117

118

119

120

121

122

123

124

125

126

TABLE 6 No. Structure 127

128

Preferably X is selected from the group consisting of

(CH₃)₂—aryl, C₅-C₆cycloalkyl)₂CCN, (C₁-C₁₂alkyl)₂CCN, —CH₂CH═CH₂,(C₁-C₁₂)alkyl-CR₂₀—C(O)—(C₁-C₁₂alkyl,(C₁-C₁₂)alkyl-CR₂₀—C(O)—(C₆-C₁₀aryl,(C₁-C₁₂)alkyl-CR₂₀—C(O)—(C₁-C₁₂)alkoxy, (C₁-C₁₂)alkyl-CR₂₀—C(O)-phenoxy,(C₁-C₁₂)alkyl-CR₂₀—C(O)—N-di(C₁-C₁₂)alkyl,(C₁-C₁₂)alkyl-CR₂₀—CO—NH(C₁-C₁₂)alkyl, (C₁-C₁₂)alkyl-CR₂₀—CO—NH₂,—CH₂CH═CH—CH₃, —CH₂—C(CH₃)═CH₂, —CH₂—

wherein

R₂₀ is hydrogen or C₁-C₁₂alkyl;

the aryl groups are unsubstituted or substituted with C₁-C₁₂alkyl,halogen, C₁-C₁₂alkoxy, C₁-C₁₂alkylcarbonyl, glycidyloxy, OH, —COOH or—COOC₁-C₁₂alkyl.

More preferred are compounds, wherein X is selected from the groupconsisting of —CH₂-phenyl, —CH₃CH-phenyl, (CH₃)₂C-phenyl,(C₅-C₆cycloalkyl)₂CCN, (CH₃)₂CCN, —CH₂CH═CH₂, CH₃CH—CH═CH₂,(C₁-C₈alkyl)CR₂₀—C(O)-phenyl, (C₁-C₈)alkyl-CR₂₀—C(O)—(C₁-C₈)alkoxy,(C₁-C₈)alkyl-CR₂₀—C(O)—(C₁-C₈)alkyl,(C₁-C₈)alkyl-CR₂₀—C(O)—N-di(C₁-C₈)alkyl,(C₁-C₈)alkyl-CR₂₀—C(O)—NH(C₁-C₈)alkyl, (C₁-C₈)alkyl-CR₂₀—C(O)—NH₂,wherein R₂₀ is hydrogen or (C₁-C₈)alkyl.

Particularly preferred are compounds, wherein X is selected from thegroup consisting of —CH₂-phenyl, —CH₃CH-phenyl, (CH₃)₂C-phenyl,(C₅-C₆cycloalkyl)₂CCN, (CH₃)₂CCN, —CH₂CH═CH₂, CH₃CH—CH═CH₂,(C₁-C₄alkyl)CR₂₀—C(O)-phenyl, (C₁-C₄)alkyl-CR₂₀—C(O)—(C₁-C₄)alkoxy,(C₁-C₄)alkyl-CR₂₀—C(O)—(C₁-C₄)alkyl,(C₁-C₄)alkyl-CR₂₀—C(O)—N-di(C₁-C₄)alkyl,(C₁-C₄)alkyl-CR₂₀—C(O)—NH(C₁-C₄)alkyl, (C₁-C₄)alkyl-CR₂₀—C(O)—NH₂,wherein R₂₀ is hydrogen or (C₁-C₄)alkyl.

Another embodiment of the present invention is a composition, whereincomponent b3) is present as an alternative for b1) or b2).

A suitable component b3) contains a compound of formula (III),

with a radically transferable atom or group ·Hal as is described in WO96/30421 and WO 98/01480. A preferred radically transferable atom orgroup ·Hal is ·Cl or ·Br, which is cleaved as a radical from theinitiator molecule.

Preferably [In] represents the polymerization initiator fragment of apolymerization initiator of formula (III),

capable of initiating polymerization of monomers or oligomers whichpolymerization initiator is selected from the group consisting ofC₁-C₈-alkyl halides, C₆-C₁₅-aralkylhalides, C₂-C₈α-haloalkyl esters,arene sulfonyl chlorides, haloalkanenitrites, α-haloacrylates andhalolactones, p and q represent one and the other components are asdefined above.

The polymerization process in the presence of a compound of formula(III) is known as ATRP (Atom Transfer Radical Polymerization) and WO96/30421 discloses a controlled or “living” polymerization process ofethylenically unsaturated polymers such as styrene or (meth)acrylates byemploying the ATRP method. According to this method initiators areemployed which generate a radical atom such as ·Cl, in the presence of aredox system of transition metals of different oxidation states, e.g.Cu(I) and Cu(II), providing “living” or controlled radicalpolymerization.

Specific initiators are selected from the group consisting ofα,α′-dichloro- or α,α′-dibromoxylene, p-toluenesulfonylchloride (PTS),hexakis-(α-chloro- or α-bromomethyl)-benzene, 2-chloro- or2-bromopropionic acid, 2-chloro- or 2-bromoisobutyric acid, 1-phenethylchloride or bromide, methyl or ethyl 2-chloro- or 2-bromopropionate,ethyl-2-bromo- or ethyl-2-chloroisobutyrate, chloro- orbromoacetonitrile, 2-chloro- or 2-bromopropionitrile,α-bromo-benzacetonitrile and α-bromo-γ-butyrolactone(=2-bromo-dihydro-2(3H)-furanone).

The transition metal in the oxidizable transition metal complex catalystsalt used in the process of the invention is present as an oxidizablecomplex ion in the lower oxidation state of a redox system. Preferredexamples of such redox systems are selected from the group consisting ofGroup V(B), VI(B), VII(B), VIII, IB and IIB elements, such as Cu⁺/Cu²⁺,Cu⁰/Cu⁺, Fe⁰/Fe²⁺, Fe²⁺/Fe³⁺, Ru²⁺/Ru³⁺, Ru³⁺/Ru⁴⁺, Os²⁺/Os³⁺,V^(n+)/V^((n+1)+), Cr²⁺/Cr³⁺, Co⁺/Co²⁺, Co²⁺/Co³⁺, Ni⁰/Ni⁺, Ni⁺/Ni²⁺,Ni²⁺/Ni³⁺, Mn⁰/Mn²⁺, Mn²⁺/Mn³⁺, Mn³⁺/Mn⁴⁺, or Zn⁺/Zn²⁺.

The ionic charges are counterbalanced by anionic ligands commonly knownin complex chemistry of transition metals, such hydride ions (H⁻) oranions derived from inorganic or organic acids, examples being halides,e.g. F⁻, Cl⁻, Br⁻ or I⁻, fluoro complexes of the type BF₄ ⁻, PF₆ ⁻, SbF₆⁻ or AsF₆ ⁻, anions of oxygen acids, alcoholates or acetylides or anionsof cyclopentadiene.

Anions of oxygen acids are, for example, sulfate, phosphate,perchlorate, perbromate, periodate, antimonate, arsenate, nitrate,carbonate, the anion of a C₁-C₈carboxylic acid, such as formate,acetate, propionate, butyrate, benzoate, phenylacetate, mono-, di- ortrichloro- or -fluoroacetate, sulfonates, for example methylsulfonate,ethylsulfonate, propylsulfonate, butylsulfonate,trifluoromethylsulfonate (triflate), unsubstituted or C₁-C₄alkyl-,C₁-C₄alkoxy- or halo-, especially fluoro-, chloro- or bromo-substitutedphenylsulfonate or benzylsulfonate, for example tosylate, mesylate,brosylate, p-methoxy- or p-ethoxyphenylsulfonate,pentafluorophenylsulfonate or 2,4,6-triisopropylsulfonate, phosphonates,for example methylphosphonate, ethylphosphonate, propylphosphonate,butylphosphonate, phenylphosphonate, p-methylphenylphosphonate orbenzylphosphonate, carboxylates derived from a C₁-C₈carboxylic acid, forexample formate, acetate, propionate, butyrate, benzoate, phenylacetate,mono-, di- or trichloro- or -fluoroacetate, and also C₁-C₁₂-alcoholates,such as straight chain or branched C₁-C₁₂-alcoholates, e.g. methanolateor ethanolate. Anionic ligands and neutral may also be present up to thepreferred coordination number of the complex cation, especially four,five or six. Additional negative charges are counterbalanced by cations,especially monovalent cations such as Na⁺, K⁺, NH₄ ⁺ or (C₁-C₄alkyl)₄N⁺.

Suitable neutral ligands are inorganic or organic neutral ligandscommonly known in complex chemistry of transition metals. Theycoordinate to the metal ion through a σ-, π-, μ-, η-type: bonding or anycombinations thereof up to the preferred coordination number of thecomplex cation. Suitable inorganic ligands are selected from the groupconsisting of aquo (H₂O), amino, nitrogen, carbon-monoxide and nitrosyl.Suitable organic ligands are selected from the group consisting ofphosphines, e.g. (C₆H₅)₃P, (i-C₃H₇)₃P, (C₅H₉)₃P or (C₆H₁₁)₃P, di-, tri-,tetra- and hydroxyamines, such as ethylenediamine,ethylenediaminotetraacetate (EDTA),N,N-Dimethyl-N′,N′-bis(2-dimethylaminoethyl)-ethylenediamine (Me₆TREN),catechol, N,N′-dimethyl-1,2-benzenediamine, 2-(methylamino)phenol,3-(methylamino)-2-butanol orN,N′-bis(1,1-dimethylethyl)-1,2-ethanediamine,N,N,N′,N″,N″-pentamethyldiethyltriamine (PMDETA), C₁-C₈-glycols orglycerides, e.g. ethylene or propylene glycol or derivatives thereof,e.g. di-, tri- or tetraglyme, and monodentate or bidentate heterocyclice⁻ donor ligands.

Heterocyclic e⁻ donor ligands are derived, for example, fromunsubstituted or substituted heteroarenes from the group consisting offuran, thiophene, pyrrole, pyridine, bis-pyridine, picolylimine,g-pyran, g-thiopyran, phenanthroline, pyrimidine, bis-pyrimidine,pyrazine, indole, coumarone, thionaphthene, carbazole, dibenzofuran,dibenzothiophene, pyrazole, imidazole, benzimidazole, oxazole, thiazole,bis-thiazole, isoxazole, isothiazole, quinoline, bis-quinoline,isoquinoline, bis-isoquinoline, acridine, chromene, phenazine,phenoxazine, phenothiazine, triazine, thianthrene purine, bis-imidazoleand bis-oxazole.

The oxidizable transition metal complex catalyst can be formed in aseparate preliminary reaction step from its ligands or is preferablyformed in-situ from its transition metal salt, e.g. Cu(I)Cl, which isthen converted to the complex compound by addition of compoundscorresponding to the ligands present in the complex catalyst, e.g. byaddition of ethylenediamine, EDTA, Me₆TREN or PMDETA.

Preferred is a composition, wherein in the component b3) the oxidizabletransition metal in the transition metal complex salt is present as atransition metal complex ion in the lower oxidation state of a redoxsystem.

More preferred is a composition, wherein the transition metal complexion is a Cu(I) complex ion in the Cu(I)/Cu(II) system.

Another subject of the invention is a process for preparing an oligomer,cooligomer, polymer or copolymer with a polydispersity M_(w)/M_(n)between 1 and 3, which process comprises reacting a composition of a) atleast one compound of formula (I)

(RG)—A—(Stab)  (I),

wherein

(Stab) is a light stabilizer radical selected from the group consistingof sterically hindered amines, hydroxyphenyl-s-triazines,hydroxyphenyl-benzotriazols and o-hydroxybenzophenones; A is a spacergroup or a direct bond; and

(RG) is a group containing at least one ethylenically unsaturatedfunctional group; with either b1) a compound of formula (II)

X—Y  (II),

 wherein

X represents a group having at least one carbon atom and is such thatthe free radical derived from X is capable of initiating polymerizationand

Y represents a group being such that the free radical derived from itforms a stable free radical or b2) a free radical source from which aradical X· is formed capable of initiating polymerization and a stablefree radical Y·; or b3) a compound of formula (III)

 and a catalytically effective amount of an oxidizable transition metalcomplex catalyst, wherein

p represents a number greater than zero and defines the number ofinitiator fragments;

q represents a numeral greater than zero;

[In] represents a radically transferable atom or group capable ofinitiating polymerization and -[Hal] represents a leaving group; andoptionally simultaneously or in a subsequent step with c) one or moreethylenically unsaturated monomers or oligomers different from those offormula (I), at a temperature between 50° C. and 180° C.

Preferably the temperature ranges from about 80° C. to about 150° C. Attemperatures above about 180° C., the controlled conversion of themonomers into polymers may decrease, and undesirable by-products likethermally initiated polymers are formed or decomposition of thecomponents may occur.

The isolating step of the present process may be carried out by knownprocedures, e.g. by precipitation, distilling and filtering offunreacted monomer. After completing the reaction catalyst salts may befiltered off, followed by evaporation of the solvent or by precipitationof polymer in a suitable liquid phase, filtering the precipitatedpolymer, washing and drying.

The resulting oligomers, polymers, cooligomers and copolymers have anarrow molecular weight distribution. Preferably the polydispersityM_(w)/M_(n) is between 1.0 and 2, more preferably between 1.0 and 1.5and most preferably between 1.0 and 1.4.

Preferred molecular weights M_(n) are between 1000 and 50 000, morepreferred between 1000 and 10 000 and most preferred between 1000 and 5000.

The process may be carried out in the presence of an organic solvent orin the presence of water or in mixtures of organic solvents and water.Additional cosolvents or surfactants, such as glycols or ammonium saltsof fatty acids, may be present. Other suitable cosolvents are describedhereinafter.

If organic solvents are used, suitable solvents or mixtures of solventsare typically pure alkanes (hexane, heptane, octane, isooctane),aromatic hydrocarbons (benzene, toluene, xylene), halogenatedhydrocarbons (chlorobenzene), alkanols (methanol, ethanol, ethyleneglycol, ethylene glycol monomethyl ether), esters (ethyl acetate,propyl, butyl or hexyl acetate) and ethers (diethyl ether, dibutylether, ethylene glycol dimethyl ether), or mixtures thereof.

The aqueous polymerization reactions can be supplemented with awater-miscible or hydrophilic cosolvent to help ensure that the reactionmixture remains a homogeneous single phase throughout the monomerconversion. Any water-soluble or water-miscible cosolvent may be used,as long as the aqueous solvent medium is effective in providing asolvent system which prevents precipitation or phase separation of thereactants or polymer products until after all polymerization reactionshave been completed. Exemplary cosolvents useful in the presentinvention may be selected from the group consisting of aliphaticalcohols, glycols, ethers, glycol ethers, pyrrolidines, N-alkylpyrrolidinones, N-alkyl pyrrolidones, polyethylene glycols,polypropylene glycols, amides, carboxylic acids and salts thereof,esters, organosulfides, sulfoxides, sulfones, alcohol derivatives,hydroxyether derivatives such as butyl carbitol or cellosolve, aminoalcohols, ketones, and the like, as well as derivatives thereof andmixtures thereof. Specific examples include methanol, ethanol, propanol,dioxane, ethylene glycol, propylene glycol, diethylene glycol, glycerol,dipropylene glycol, tetrahydrofuran, and other water-soluble orwater-miscible materials, and mixtures thereof. When mixtures of waterand water-soluble or water-miscible organic liquids are selected as theaqueous reaction media, the water to cosolvent weight ratio is typicallyin the range of about 100:0 to about 10:90.

If more than one polymerizable compound of formula (I) is used,copolymers with different light stabilizer structures are formed. Thesecopolymers may be either random or block copolymers. Because the presentpolymerization is a “living” polymerization, it can be started andstopped practically at will. Furthermore, the polymer product retainsthe functional alkoxyamine group or the -Hal group allowing acontinuation of the polymerization in a living matter. Thus, in oneembodiment of this invention, once the first polymerizable compound offormula (I) is consumed in the initial polymerizing step a secondpolymerizable compound of formula (I) can then be added to form a secondblock on the growing polymer chain in a second polymerization step.Therefore it is possible to carry out additional polymerizations withthe same or different compounds of formula (I) or with other suitablemonomers to prepare multi-block copolymers. Furthermore, since this is aradical polymerization, blocks can be prepared in essentially any order.One is not necessarily restricted to preparing block copolymers wherethe sequential polymerizing steps must flow from the least stabilizedpolymer intermediate to the most stabilized polymer intermediate, suchas is the case in ionic polymerization.

The process is particularly useful for the preparation of blockcopolymers containing different light stabilizer groups in blocks in thecopolymer. A typical example is a block copolymer containing ahydroxy-phenyl-benzotriazol or a hydroxy-phenyl-s-triazine UV-absorberin one block whereas the other block is build from a2,2,6,6,-tertamethyl-piperidine group.

In addition to the polymerizable compounds of formula (I) conventionalmonomers can be used as comonomers, which may be desirable in somecases.

Suitable amounts of other comonomers c) are from 1% to 50% by weightbased on total monomers.

Suitable ethylenically unsaturated monomers or oligomers have beenalready given.

The initiator/regulator compound b1) is preferably present in an amountof from 0.1 mol-% to 30 mol-%, more preferably in an amount of from 0.1mol-% to 20 mol-%, and most preferably in an amount of from 0.5 mol-% to10 mol-% based on the monomer or monomer mixture.

The majority of compounds of formula (Ia) to (Ij) are known and can beprepared according to standard methods.

Examples wherein the light stabilizer is a hydroxy-phenyl-triazine aregiven in EP-A-0 434 608, U.S. Pat. No. 5,189,084 or U.S. Pat. No.5,672,704. Examples wherein the light stabilizer is ahydroxy-phenyl-benzotriazole are given in U.S. Pat. No. 4,785,063 orU.S. Pat. No. 5,112,912. Examples of suitable functionalizedbenzophenones are given in J. Polym. Sci. (1982), 27(7), 2605-13.

Polymerizable sterically hindered amines(2,2,6,6-tetramethyl-piperidines) are for example disclosed in U.S. Pat.No. 4,210,612, U.S. Pat. No. 4,294,949 or U.S. Pat. No. 4,276,401.

Polymerizable sterically hindered amines from the classes ofmorpholinone, piperazinone and piperazindione are disclosed in WO99/14206, GB 2 333 774 and GB 9913511.3.

Definitions and preferences for the different groups and substituentshave been given above, they apply also for the process.

The source of radicals in component b2) may be a bis-azo compound, aperoxide or a hydroperoxide.

Preferably, the source of radicals is 2,2′-azobisisobutyronitrile,2,2′-azobis(2-methylbutyronitrile),2,2′-azobis(2,4-dimethylvaleronitrile),2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile),1,1′-azobis(1-cyclohexanecarbonitrile),2,2′-azobis(isobutyramide)dihydrate,2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile,dimethyl-2,2′-azobisisobutyrate, 2-(carbamoylazo)isobutyronitrile,2,2′-azobis(2,4,4-trimethylpentane), 2,2′-azobis(2-methylpropane),2,2′-azobis(N,N′-dimethyleneisobutyramidine), free base orhydrochloride, 2,2′-azobis(2-amidinopropane), free base orhydrochloride,2,2′-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)ethyl]propionamide} or2,2′-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide.

Preferred peroxides and hydroperoxides are acetyl cyclohexane sulphonylperoxide, diisopropyl peroxy dicarbonate, t-amyl perneodecanoate,t-butyl perneodecanoate, t-butyl perpivalate, t-amylperpivalate,bis(2,4-dichlorobenzoyl)peroxide, diisononanoyl peroxide, didecanoylperoxide, dioctanoyl peroxide, dilauroyl peroxide, bis(2-methylbenzoyl)peroxide, disuccinic acid peroxide, diacetyl peroxide, dibenzoylperoxide, t-butyl per 2-ethylhexanoate, bis-(4-chlorobenzoyl)-peroxide,t-butyl perisobutyrate, t-butyl permaleinate,1,1-bis(t-butylperoxy)3,5,5-trimethylcyclohexane,1,1-bis(t-butylperoxy)cyclohexane, t-butyl peroxy isopropyl carbonate,t-butyl perisononaoate, 2,5-dimethylhexane 2,5-dibenzoate, t-butylperacetate, t-amyl perbenzoate, t-butyl perbenzoate, 2,2-bis(t-butylperoxy) butane, 2,2 bis (t-butylperoxy) propane, dicumylperoxide, 2,5-dimethylhexane-2,5-di-t-butylperoxide, 3-t-butylperoxy3-phenylphthalide, di-t-amyl peroxide, α,α′-bis(t-butylperoxyisopropyl)benzene, 3,5-bis(t-butylperoxy)3,5-dimethyl 1,2-dioxolane,di-t-butyl peroxide, 2,5-dimethylhexyne-2,5-di-t-butylperoxide,3,3,6,6,9,9-hexamethyl 1,2,4,5-tetraoxa cyclononane, p-menthanehydroperoxide, pinane hydroperoxide, diisopropylbenzenemono-α-hydroperoxide, cumene hydroperoxide or t-butyl hydroperoxide.

These compounds are commercially available.

If more than one radical source is used, a mixture of substitutionpatterns is obtainable.

If b2) a free radical source and a stable free radical are appliedseparately, the stable free radical is preferably present in an amountof from 0.1 mol-% to 30 mol-%, more preferably in an amount of from 0.1mol-% to 20 mol-%, and most preferably in an amount of from 0.5 mol-% to10 mol-% based on the monomer or monomer mixture.

The molar ratio of the radical source to the stable nitroxyl radical maybe from 1:10 to 10:1, preferably from 1:5 to 5:1 and more preferablyfrom 1:2 to 2:1.

If b3) is applied, the compound of formula (III)

is preferably present in an amount of from 0.1 mol-% to 30 mol-%, morepreferably in an amount of from 0.1 mol-% to 20 mol-%, and mostpreferably in an amount of from 0.5 mol-% to 10 mol-% based on themonomer or monomer mixture.

A catalytically effective amount of an oxidizable transition metalcomplex catalyst is preferably 100 ppm to 1%, more preferably 100 ppm to5000 ppm based on the monomer or monomer mixture. Preferably the molarratio of complexing agent to transition metal is from 1:5 to 5:1, morepreferably from 2:1 to 1:2.

If the process b3) is applied the resulting polymer oligomer contains atits end a halogen atom. This halogen atom can be exchanged by reacting astable free radical Y· with the oligomer or polymer. In this case thefree radical is attached to the polymer and the halogen atom is removed.The exchange process is described in PCT/EP 99/06924.

Another subject of the invention is a oligomer, polymer, cooligomercopolymer obtainable by the above mentioned processes.

Still another subject of the invention are the compounds1,1,3,3-Tetraethyl-2-(1-phenyl-ethoxy)-2,3-dihydro-1.H.-isoindole,1-(1,1,3,3-Tetraethyl-1,3-dihydro-isoindol-2-yloxy)-cyclohexanecarbonitrileorN-(1,1,3,3-tetramethyl-butyl)-N,O-bis-(1-cyano-1-methyl-ethyl)-hydroxylamin.These compounds used as polymerization regulators PR3, PR4 and PR5 arenew.

The oligomers, polymers cooligomers or copolymers obtained by thepresent process are useful as light or heat stabilizers, particularUV-light stabilizers of organic materials. Preferred organic materialsare natural or synthetic polymers. Examples are given below.

The term heat or light stabilizer in the context of the presentinvention means stabilization against the influences of heat and/oractinic or electromagnetic radiation ranging from γ to infrared.

1. Polymers of monoolefins and diolefins, for example polypropylene,polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyisoprene orpolybutadiene, as well as polymers of cycloolefins, for instance ofcyclopentene or norbornene, polyethylene (which optionally can becrosslinked), for example high density polyethylene (HDPE), high densityarid high molecular weight polyethylene (HDPE-HMW), high density andultrahigh molecular weight polyethylene (HDPE-UHMW), medium densitypolyethylene (MDPE), low density polyethylene (LDPE), linear low densitypolyethylene (LLDPE), (VLDPE) and (ULDPE).

Polyolefins; i.e. the polymers of monoolefins exemplified in thepreceding paragraph, preferably polyethylene and polypropylene, can beprepared by different, and especially by the following, methods:

a) radical polymerization (normally under high pressure and at elevatedtemperature).

b) b catalytic polymerization using a catalyst that normally containsone or more than one metal of groups IVb, Vb, VIb or VIII of thePeriodic Table.These metals usually have one or more than one ligand,typically oxides, halides, alcoholates, esters, ethers, amines, alkyls,alkenyls and/or aryls that may be either π- or σ-coordinated. Thesemetal complexes may be in the free form or fixed on substrates,typically on activated magnesium chloride, titanium(III) chloride,alumina or silicon oxide. These catalysts may be soluble or insoluble inthe polymerization medium. The catalysts can be used by themselves inthe polymerization or further activators may be used, typically metalalkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metalalkyloxanes, said metals being elements of groups Ia, IIa and/or, IIIaof the Periodic Table. The activators may be modified conveniently withfurther ester, ether, amine or silyl ether groups. These catalystsystems are usually termed Phillips, Standard Oil Indiana, Ziegler(-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).

2. Mixtures of the polymers mentioned under 1), for example mixtures ofpolypropylene with polyisobutylene, polypropylene with polyethylene (forexample PP/HDPE, PP/LDPE) and mixtures of different types ofpolyethylene (for example LDPE/HDPE).

3. Copolymers of monoolefins and diolefins with each other or with othervinyl monomers, for example ethylene/propylene copolymers, linear lowdensity polyethylene (LLDPE) and mixtures thereof with low density.polyethylene (LDPE), propylene/but-1-ene copolymers,propylene/isobutylene copolymers, ethylene/but-1-ene copolymers,ethylene/hexene copolymers, ethylene/methylpentene copolymers,ethylene/heptene copolymers, ethylene/octene copolymers,propylene/butadiene copolymers, isobutylene/isoprene copolymers,ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylatecopolymers, ethylene/vinyl acetate copolymers and their copolymers withcarbon monoxide or ethylene/acrylic acid copolymers and their salts(ionomers) as well as terpolymers of ethylene with propylene and a dienesuch as hexadiene, dicyclopentadiene or ethylidene-norbornene; andmixtures of such copolymers with one another and with polymers mentionedin 1) above, for example polypropylene/ethylene-propylene copolymers,LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acidcopolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or randompolyalkylene/carbon monoxide copolymers and mixtures thereof with otherpolymers, for example polyamides.

4. Hydrocarbon resins (for example C₅-C₉) including hydrogenatedmodifications thereof (e.g. tackifiers) and mixtures of polyalkylenesand starch.

5. Polystyrene, poly(p-methylstyrene), poly(α-methylstyrene).

6. Copolymers of styrene or α-methylstyrene with dienes or acrylicderivatives, for example styrene/butadiene, styrene/acrylonitrile,styrene/alkyl methacrylate, styrene/butadiene/alkyl acrylate,styrene/butadiene/alkyl methacrylate, styrene/maleic anhydride,styrene/acrylonitrile/methyl acrylate; mixtures of high impact strengthof styrene copolymers and another polymer, for example a polyacrylate, adiene polymer or an ethylene/propylene/diene terpolymer; and blockcopolymers of styrene such as styrene/butadiene/styrene,styrene/isoprene/styrene, styrene/ethylene/butylene/styrene orstyrene/ethylene/propylene/styrene.

7. Graft copolymers of styrene or α-methylstyrene, for example styreneon polybutadiene, styrene on polybutadiene-styrene orpolybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (ormethacrylonitrile) on polybutadiene; styrene, acrylonitrile and methylmethacrylate on polybutadiene; styrene and maleic anhydride onpolybutadiene; styrene, acrylonitrile and maleic anhydride or maleimideon polybutadiene; styrene and maleimide on polybutadiene; styrene andalkyl acrylates or methacrylates on polybutadiene; styrene andacrylonitrile on ethylene/propylene/diene terpolymers; styrene andacrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styreneand acrylonitrile on acrylate/butadiene copolymers, as well as mixturesthereof with the copolymers listed under 6), for example the copolymermixtures known as ABS, MBS, ASA or AES polymers.

8. Halogen-containing polymers such as polychloroprene, chlorinatedrubbers, chlorinated and brominated copolymer of isobutylene-isoprene(halobutyl rubber), chlorinated or sulfochlorinated polyethylene,copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo-and copolymers, especially polymers of halogen-containing vinylcompounds, for example polyvinyl chloride, polyvinylidene chloride,polyvinyl fluoride, polyvinylidene fluoride, as well as copolymersthereof such as vinyl chloride/vinylidene chloride, vinyl chloride/vinylacetate or vinylidene chloride/vinyl acetate copolymers.

9. Polymers derived from α,β-unsaturated acids and derivatives thereofsuch as polyacrylates and polymethacrylates; polymethyl methacrylates,polyacrylamides and polyacrylonitriles, impact-modified with butylacrylate.

10. Copolymers of the monomers mentioned under 9) with each other orwith other unsaturated monomers, for example acrylonitrile/butadienecopolymers, acrylonitrile/alkyl acrylate copolymers,acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl-halidecopolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers.

11. Polymers derived from unsaturated alcohols and amines or the acylderivatives or acetals thereof, for example polyvinyl alcohol, polyvinylacetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate,polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well astheir copolymers with olefins mentioned in 1) above.

12. Homopolymers and copolymers of cyclic ethers such as polyalkyleneglycols, polyethylene oxide, polypropylene oxide or copolymers thereofwith bisglycidyl ethers.

13. Polyacetals such as polyoxymethylene and those polyoxymethyleneswhich contain ethylene oxide as a comonomer; polyacetals modified withthermoplastic polyurethanes, acrylates or MBS.

14. Polyphenylene oxides and sulfides, and mixtures of polyphenyleneoxides with styrene polymers or polyamides.

15. Polyurethanes derived from hydroxyl-terminated polyethers,polyesters or polybutadienes on the one hand and aliphatic or aromaticpolyisocyanates on the other, as well as precursors thereof.

16. Polyamides and copolyamides derived from diamines and dicarboxylicacids and/or from aminocarboxylic acids or the corresponding lactams,for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12,4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides startingfrom m-xylene diamine and adipic acid; polyamides prepared fromhexamethylenediamine and isophthalic or/and terephthalic acid and withor without an elastomer as modifier, for examplepoly-2,4,4,-trimethylhexamethylene terephthalamide or poly-m-phenyleneisophthalamide; and also block copolymers of the aforementionedpolyamides with polyolefins, olefin copolymers, ionomers or chemicallybonded or grafted elastomers; or with polyethers, e.g. with polyethyleneglycol, polypropylene glycol or polytetramethylene glycol; as well aspolyamides or copolyamides modified with EPDM or ABS; and polyamidescondensed during processing (RIM polyamide systems).

17. Polyureas, polyimides, polyamide-imides, polyetherimids,polyesterimids, polyhydantoins and polybenzimidazoles.

18. Polyesters derived from dicarboxylic acids and diols and/or fromhydroxycarboxylic acids or the corresponding lactones, for examplepolyethylene terephthalate, polybutylene terephthalate,poly-1,4-dimethylolcyclohexane terephthalate and polyhydroxybenzoates,as well as block copolyether esters derived from hydroxyl-terminatedpolyethers; and also polyesters modified with polycarbonates or MBS.

19. Polycarbonates and polyester carbonates.

20. Polysulfones, polyether sulfones and polyether ketones.

21. Crosslinked polymers derived from aldehydes on the one hand andphenols, ureas and melamines on the other hand, such asphenol/formaldehyde resins, urea/formaldehyde resins andmelamine/formaldehyde resins.

22. Drying and non-drying alkyd resins.

23. Unsaturated polyester resins derived from copolyesters of saturatedand unsaturated dicarboxylic acids with polyhydric alcohols and vinylcompounds as crosslinking agents, and also halogen-containingmodifications thereof of low flammability.

24. Crosslinkable acrylic resins derived from substituted acrylates, forexample epoxy acrylates, urethane acrylates or polyester acrylates.

25. Alkyd resins, polyester resins and acrylate resins crosslinked withmelamine resins, urea resins, isocyanates, isocyanurates,polyisocyanates or epoxy resins.

26. Crosslinked epoxy resins derived from aliphatic, cycloaliphatic,heterocyclic or aromatic glycidyl compounds, e.g. products of diglycidylethers of bisphenol A and bisphenol F, which are crosslinked withcustomary hardeners such as anhydrides or amines, with or withoutaccelerators.

27. Natural polymers such as cellulose, rubber, gelatin and chemicallymodified homologous derivatives thereof, for example cellulose acetates,cellulose propionates and cellulose butyrates, or the cellulose etherssuch as methyl cellulose; as well as rosins and their derivatives.

28. Blends of the aforementioned polymers (polyblends), for examplePP/EPDM, Polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS,PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR,PC/thermoplazstic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 andcopolymers, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.

Still a further subject of the present invention is the use of aoligomer, polymer, cooligomer, or copolymer of formula (III), (IIIa);(IIIb), (IIIc), (IIId), (IIIe) or (IIIf) as light stabilizers fororganic materials, particularly for natural and synthetic polymers.

Most preferred are thermoplastic polymers and crosslinked polymers, suchas thermosetting enamels, paints, laquers and varnishes.

Also subject of the present invention are organic materials stabilizedagainst UV-light with a oligomer, polymer, cooligomer or copolymer offormula (III), (IIIa), (IIIb), (IIIc), (IIId), (IIIe) or (IIIf).

The organic material may contain additional additives and stabilizers.Examples are given below.

1. Antioxidants

1.1. Alkylated monophenols, for example2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-di-methylphenol,2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol,2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol,2-(α-methylcyclohexyl)-4,6-dimethyl-phenol,2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol,2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenois which are linearor branched in the side chains, for example,2,6-di-nonyl-4-methylphenol,2,4-dimethyl-6-(1′-methylundec-1′-yl)phenol,2,4-dimethyl-6-(1′-methylheptadec-1′-yl)phenol,2,4-dimethyl-6-(1′-methyltridec-1′-yl)phenol and mixtures thereof.

1.2. Alkylthiomethylphenols, for example2,4-dioctylthiomethyl-6-tert-butylphenol,2,4-dioctylthiomethyl-6-methylphenol,2,4-dioctylthiomethyl-6-ethylphenol,2,6-di-dodecylthiomethyl-4-nonylphenol.

1.3. Hydroquinones and alkylated hydroquinones, for example2,6-di-tert-butyl-4-methoxy-phenol, 2,5-di-tert-butylhydroquinone,2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol,2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole,3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenylstearate, bis-(3,5-di-tert-butyl-4-hydroxyphenyl) adipate.

1.4. Tocopherols, for example α-tocopherol, β-tocopherol, γ-tocopherol,δ-tocopherol and mixtures thereof (Vitamin E).

1.5. Hydroxylated thiodiphenyl ethers, for example2,2′-thiobis(6-tert-butyl-4-methylphenol), 2,2′-thiobis(4-octylphenol),4,4′-thiobis(6-tert-butyl-3-methylphenol),4,4′-thiobis(6-tert-butyl-2-methylphenol),4,4′-thiobis-(3,6-di-sec-amylphenol),4,4′-bis(2,6-dimethyl-4-hydroxyphenyl)disulfide.

1.6. Alkylidenebisphenols, for example2,2′-methylenebis(6-tert-butyl-4-methylphenol),2,2′-methylenebis(6-tert-butyl-4-ethylphenol),2,2′-methylenebis[4-methyl-6-(α-methylcyclohexyl)-phenol],2,2′-methylenebis(4-methyl-6-cyclohexylphenol),2,2′-methylenebis(6-nonyl-4-methylphenol),2,2′-methylenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(6-tert-butyl-4-isobutylphenol),2,2′-methylenebis[6-(α-methylbenzyl)-4-nonylphenol],2,2′-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol],4,4′-methylenebis(2,6-di-tert-butylphenol),4,4′-methylenebis(6-tert-butyl-2-methylphenol),1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol,1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,1,1-bis(5-tert-butyl-4-hydroxy-2-methyl-phenyl)-3-n-dodecylmercaptobutane,ethylene glycol bis[3,3-bis(3′-tert-butyl-4′-hydroxyphenyl)butyrate],bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopentadiene,bis[2-(3′-tert-butyl-2′-hydroxy-5′-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate,1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane,2,2-bis-(3,5-di-tert-butyl-4-hydroxyphenyl)propane,2,2-bis-(5-tert-butyl-4-hydroxy2-methylphenyl)-4-n-dodecylmercaptobutane,1,1,5,5-tetra-(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.

1.7. O-, N- and S-benzyl compounds, for example3,5,3′,5′-tetra-tert-butyl-4,4′-dihydroxydibenzyl ether,octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate,tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate,tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine,bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate,bis(3,5-di-tert-butyl-4-hydroxy-benzyl)sulfide,isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.

1.8. Hydroxybenzylated malonates, for exampledioctadecyl-2,2-bis-(3,5-di-tert-butyl-2-hydroxybenzyl)-malonate,di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)-malonate,di-dodecylmercaptoethyl-2,2-bis-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate,bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.

1.9. Aromatic hydroxybenzyl compounds, for example1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene,2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.

1.10. Triazine Compounds, for example2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine,2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine,1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate,2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine,1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-1,3,5-triazine,1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.

1.11. Benzylphosphonates, for exampledimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate,diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, thecalcium salt of the monoethyl ester of3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.

1.12. Acylaminophenols, for example 4-hydroxylauranilide,4-hydroxystearanilide, octylN-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.

1.13. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid withmono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol,i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol,3-thiapentadecanol, trimethylhexanediol, trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.14. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acidwith mono- or polyhydric alcohols, e.g. with methanol, ethanol,n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethyleneglycol, diethylene glycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl) isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.15. Esters of β-(3,5-dicyclohexyl-4-hydroxyphenylpropionic acid withmono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono-or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.17. Amides of β-(3,5-di-tert-butyl-4-hydroxyohenyl)propionic acid e.g.N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide,N,N′bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamide,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazide,N,N′-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxamide(Naugard®XL-1 supplied by Uniroyal).

1.18. Ascorbic acid (vitamin C)

1.19. Aminic antioxidants, for exampleN,N′-di-isopropyl-p-phenylenediamine,N,N′-di-sec-butyl-p-phenylenediamine,N,N′bis(1,4-dimethylpentyl)-p-phenylenediamine,N,N′bis(1-ethyl-3-methylpentyl)-p-phenylenediamine,N,N′bis(1-methylheptyl)-p-phenylenediamine,N,N′-dicyclohexyl-p-phenylenediamine, N,N′-diphenyl-p-phenylenediamine,N,N′bis(2-naphthyl)-p-phenylenediamine,N-isopropyl-N′-phenyl-p-phenylenediamine,N-(1,3-dimethylbutyl)-N′-phenyl-p-phenyleriediazmine,N-(1-methylheptyl)-N′-phenyl-p-phenylenediamine,N-cyclohexyl-N′-phenyl-p-phenlenediamine,4-(p-toluenesulfamoyl)diphenylamine,N,N′-dimethyl-N,N′-di-sec-butyl-p-phenylenediamine, diphenylamine,N-allyldiphenylamine, 4-isopropoxydiphenylamine,N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine,N-phenyl-2-naphthylamine, octylated diphenylamine, for examplep,p′-di-tert-octyldiphenylamine, 4-n-butylaminophenol,4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol,4-octadecanoylaminophenol, bis(4-methoxyphenyl)amine,2,6-di-tert-butyl-4-dimethylaminomethylphenol,2,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane,N,N,N′,N′-tetramethyl-4,4′-diaminodiphenylmethane,1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenylamino)propane,(o-tolyl)biguanide, bis[4-(1′,3′-dimethylbutyl)phenyl]amine,tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- anddialkylated tert-butyl/tert-octyldiphenylamines, a mixture of mono- anddialkylated nonyldiphenylamines, a mixture of mono- and dialkylateddodecyldiphenylamines, a mixture of mono- and dialkylatedisopropyl/isohexyldiphenylamines, a mixture of mono- und dialkylatedtert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine,phenothiazine, a mixture of mono- und dialkylatedtert-butyl/tert-octylphenothiazines, a mixture of mono- und dialkylatedtert-octyl-phenothiazines, N-allylphenothiazin,N,N,N′,N′-tetraphenyl-1,4-diaminobut-2-ene,N,N-bis-(2,2,6,6-tetramethyl-piperid-4-yl-hexamethylenediamine,bis(2,2,6,6-tetramethylpiperid-4-yl)sebacate,2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol.

2. UV Absorbers and Light Stabilisers

2.1. 2-(2′-Hydroxyphenyl)benzotriazoles, for example2-(2′-hydroxy-5′-methylphenyl)-benzotriazole,2-(3′,5′-di-tert-butyl-2′-hydroxyphenylpenzotriazole,2-(5′-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(2′-hydroxy-5′-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole,2-(3′,5′-tert-butyl-2′-hydroxyphenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-methylphenyl)-5-chloro-benzotriazole,2-(3′-sec-butyl-5′-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(2′-hydroxy-4′-octyloxyphenyl)benzotriazole,2-(3′,5′-di-tert-amyl-2′-hydroxyphenyl)benzotriazole,2-(3′,5′-bis-(α,α-dimethylbenzyl)-2′-hydroxyphenylbenzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)-carbonylethyl]-2′-hydroxyphenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)benzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxyphenyl)benzotriazole,2-(3′-dodecyl-2′-hydroxy-5′-methylphenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-isooctyloxycarbonylethyl)phenylbenztriazole,2,2′-methylene-bis-[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazole-2-ylphenol];the transesterification product of2-[3′-tert-butyl-5′-(2-methoxycarbonylethyl)-2′-hydroxyphenyl]-2H-benzotriazolewith polyethylene glycol 300; [R—CH₂CH₂—COO—CH₂CH₂₂ whereR=3′-tert-butyl-4′-hydroxy-5′-2H-benzotriazol-2-ylphenyl,2-[2′-hydroxy-3′-(α,α-dimethylbenzyl)-5′-(1,1,3,3-tetramethylbutyl)phenyl]benzotriazole;2-[2′-hydroxy-3′-(1,1,3,3-tetramethylbutyl)-5′-(α,α-dimethylbenzyl)phenyl]benzotriazole.

2.2. 2-Hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy,4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2′,4′-trihydroxyand 2′-hydroxy-4,4′-dimethoxy derivatives.

2.3. Esters of substituted and unsubstituted benzoic acids, as forexample 4-tertbutyl-phenyl salicylate, phenyl salicylate, octylphenylsalicylate, dibenzoyl resorcinol, bis(4-tert-butylbenzoyl) resorcinol,benzoyl resorcinol, 2,4-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate.

2.4. Acrylates, for example ethyl α-cyano-β,β-diphenylacrylate, isooctylα-cyano-β,β-diphenylacrylate, methyl α-carbomethoxycinnamate, methylα-cyano-β-methyl-p-methoxy-cinnamate, butylα-cyano-β-methyl-p-methoxy-cinnamate, methylα-carbomethoxy-p-methoxycinnamate andN-(β-carbomethoxy-β-cyanovinyl)-2-methylindoline.

2.5. Nickel compounds, for example nickel complexes of2,2′-thio-bis-[4-(1,1,3,3-tetramethylbutyl)phenol], such as the 1:1 or1:2 complex, with or without additional ligands such as n-butylamine,triethanolamine or N-cyclohexyldiethanolamine, nickeldibutyldithiocarbamate, nickel salts of the monoalkyl esters, e.g. themethyl or ethyl ester, of 4-hydroxy-3,5-di-tert-butylbenzylphosphonicacid, nickel complexes of ketoximes, e.g. of 2-hydroxy-4-methylphenylundecylketoxime, nickel complexes of1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additionalligands.

2.6. Sterically hindered amines, for examplebis(2,2,6,6-tetramethyl-4-piperidyl)sebacate,bis(2,2,6,6-tetramethyl-4-piperidyl)succinate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate,bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate,bis(1,2,2,6,6-pentamethyl-4-pi-peridyl)n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, linear or cyclic condensates ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-tert-octylamino-2,6-dichloro-1,3,5-triazine,tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate,tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane-tetracarboxylate,1,1′-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone),4-benzoyl-2,2,6,6-tetramethylpiperidine,4-stearyloxy-2,2,6,6-tetramethylpiperidine,bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate,3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decan-2,4-dione,bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate,bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate, linear or cycliccondensates ofN,N′-bis-(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazineand 1,2-bis(3-aminopropylamino)ethane, the condensate of2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazineand 1,2-bis-(3-aminopropylamino)ethane,8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidin-2,5-dione,3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione, amixture of 4-hexadecyloxy- and4-stearyloxy-2,2,6,6-tetramethylpiperidine, a condensation product ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, a condensation product of1,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1,3,5-triazine aswell as 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No.[136504-96-6]), N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimid,N-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimid,2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4,5]decane, areaction product of7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro[4,5]decaneund epichlorohydrin,1,1-bis(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)-2-(4-methoxyphenyl)ethene,N,N′-bis-formyl-N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine,diester of 4-methoxymethylene-malonic acid with1,2,2,6,6-pentamethyl-4-hydroxypiperidine,poly[methylpropyl-3-oxy-4-(2,2,6,6-tetramethyl-4-piperidyl)]siloxane,reaction product of maleic acid anhydride-α-olefin-copolymer with2,2,6,6-tetramethyl-4-aminopiperidine or1,2,2,6,6-pentamethyl-4-aminopiperidine.

2.7. Oxamides, for example 4,4′-dioctyloxyoxanilide,2,2′-diethoxyoxanilide, 2,2′-dioctyloxy-5,5′-di-tert-butoxanilide,2,2′-didodecyloxy-5,5′-di-tert-butoxanilide, 2-ethoxy-2′-ethyloxanlide,N,N′-bis(3-dimethylaminopropyl)oxamide,2-ethoxy-5-tert-butyl-2′-ethoxanilide and its mixture with2-ethoxy-2′-ethyl-5,4′-di-tert-butoxanilide, mixtures of o- andp-methoxy-disubstituted oxanilides and mixtures of o- andp-ethoxy-disubstituted oxanilides.

2.8. 2-(2-Hydroxyphenyl)-1,3,5-triazines, for example2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis-(4-methylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-butyloxy-propoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-octyloxy-propyloxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine,2-[4-(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxy-phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxy-propoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine,2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine,2,4,6-tris[2-hydroxy-4-(butoxy-2-hydroxy-propoxy)phenyl]-1,3,5-triazine,2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine,2-{2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxy]phenyl}-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.

3. Metal deactivators, for example N,N′-diphenyloxamide,N-salicylal-N′-salicyloyl hydrazine, N,N′-bis(salicyloyl) hydrazine,N,N′bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine,3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide,oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide,N,N′-diacetyladipoyl dihydrazide, N,N′-bis(salicyloyl)oxalyldihydrazide, N,N′-bis(salicyloyl)thiopropionyl dihydrazide.

4. Phosphites and phosphonites, for example triphenyl phosphite,diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite,diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite,bis(2,6-di-tert-butyl-4-methylphenyl)-pentaerythritol diphosphite,diisodecyloxypentaerythritol diphosphite,bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite,bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite, tristearylsorbitol triphosphite, tetrakis(2,4-di-tert-bu-tylphenyl)4,4′-biphenylene diphosphonite,6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-1,3,2-dioxaphosphocin,6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz[d,g]-1,3,2-dioxaphosphocin,bis(2,4-di-tert-butyl-6-methylphenyl) methyl phosphite,bis(2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite,2,2′,2″-nitrilo[triethyltris(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite],2-ethylhexyl(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite.

Especially preferred are the following phosphites:

Tris(2,4-di-tert-butylphenyl) phosphite (Irgafos®168, Ciba-Geigy),tris(nonylphenyl) phosphite,

5. Hydroxylamines, for example, N,N-dibenzylhydroxylamine,N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine,N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine,N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine,N-hexadecyl-N-octadecylhydroxylamine, N-heptadecyl,N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derived fromhydrogenated tallow amine.

6. Nitrones, for example, N-benzyl-alpha-phenyl-nitrone,N-ethyl-alpha-methylnitrone, N-octyl-alpha-heptyl-nitrone,N-lauryl-alpha-undecyl-nitrone, N-tetradecyl-alpha-tridcyl-nitrone,N-hexadecyl-alpha-pentadecyl-nitrone,N-octadecyl-alpha-heptadecyl-nitrone,N-hexadecyl-alpha-heptadecyl-nitrone,N-ocatadecyl-alpha-pentadecyl-nitrone,N-heptadecyl-alpha-heptadecyl-nitrone,N-octadecyl-alpha-hexadecyl-nitrone, nitrone derived fromN,N-dialkylhydroxylamine derived from hydrogenated tallow amine.

7. Thiosynergists, for example, dilauryl thiodipropionate or distearylthiodipropionate.

8. Peroxide scavengers, for example esters of β-thiodipropionic acid,for example the lauryl, stearyl, myristyl or tridecyl esters,mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zincdibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritoltetrakis(β-dodecylmercapto)propionate.

9. Polyamide stabilisers, for example, copper salts in combination withiodides and/or phosphorus compounds and salts of divalent manganese.

10. Basic co-stabilisers, for example, melamine, polyvinylpyrrolidone,dicyandiamide, triallyl cyanurate, urea derivatives, hydrazinederivatives, amines, polyamides, polyurethanes, alkali metal salts andalkaline earth metal salts of higher fatty acids for example calciumstearate, zinc stearate, magnesium behenate, magnesium stearate, sodiumricinoleate and potassium palmitate, antimony pyrocatecholate or zinkpyrocatecholate.

11. Nucleating agents, for example, inorganic substances such as talcum,metal oxides such as titanium dioxide or magnesium oxide, phosphates,carbonates or sulfates of, preferably, alkaline earth metals; organiccompounds such as mono- or polycarboxylic acids and the salts thereof,eg. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodiumsuccinate or sodium benzoate; polymeric compounds such as ioniccopolymers (ionomers).

12. Fillers and reinforcing agents, for example, calcium carbonate,silicates, glass fibres, glass bulbs, asbestos, talc, kaolin, mica,barium sulfate, metal oxides and hydroxides, carbon black, graphite,wood flour and flours or fibers of other natural products, syntheticfibers.

13. Other additives, for example, plasticisers, lubricants, emulsifiers,pigments, rheology additives, catalysts, flow-control agents, opticalbrighteners, flameproofing agents, antistatic agents and blowing agents.

14. Benzofuranones and indolinones, for example those disclosed in U.S.Pat. No. 4,325,863; U.S. Pat. No. 4,338,244; U.S. Pat. No. 5,175,312;U.S. Pat. No. 5,216,052; U.S. Pat. No. 5,252,643; DE-A-4316611;DE-A-4316622; DE-A-4316876; EP-A-0589839 or EP-A-0591 102 or3-[4-(2-acetoxyethoxy)-phenyl]-5,7-di-tert-butyl-benzofuran-2-one,5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one,3,3′-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one],5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one,3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one,3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl-benzofuran-2-one,3-(3,4-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one,3-(2,3-di-methylphenyl)-5,7-di-tert-butyl-benzofuran-2-one.

The following examples illustrate the invention.

A) Polymerization Examples Using Compounds of Formula (II)

X—Y  (II)

General Remarks:

All monomers employed are used in purities of >99% and without anystabilisers. Accordingly, the monomers are distilled or recrystallisedimmediately before polymerization. The polymerization regulatorsemployed are recrystallised, distilled or chromatographed to be used inpurities of >99%. Solvents are also distilled under inert gas. Thepolymerization is carried out under argon gas, the polymerizationsolution being freed beforehand from oxygen by repeated evacuation undervacuum and rinsing with argon. After the polymerization, the solution isfreed from the volatile components (solvent, monomer) by vacuumdistillation at 80° C. In cases where the monomers cannot be distilled,the polymer is isolated by precipitation. The polymerization yield isthe result of the weight of the residue minus the weight of thepolymerization regulator and catalyst used. In case that viscous liquidsare obtained, catalyst residues can be removed by filtration underpressure at 80° C.

List of the polymerization regulators used:

No. Formula PR1 1-α-methylbenzyloxy-2,6-diethyl-2,3,6-trimethyl-4-oxypiperidine

PR2 N-(1,1,3,3-tetramethyl-butyl)-N,O-bis-(1-cyano-cyclohexyl)-hydroxylamin

PR3 1,1,3,3-Tetraethyl-2-(1-phenyl- ethoxy)-2,3-dihydro-1.H.-isoindole

PR4 1-(1,1,3,3-Tetraethyl-1,3-dihydro-isoindol-2-yloxy)-cyclohexanecarbonitrile

PR5 N-(1,1,3,3-tetramethyl-butyl)-N,O-bis-(1-cyano-1-methyl-ethyl)-hydroxylamin

PR6 {1-[.tert.-Butyl-(1-phenyl-ethoxy)- amino]-2,2-dimethyl-propyl)-phosphonic acid diethyl ester

PR1 is known and prepared as described in GB 2 335 190 (compound 112).

PR2 and PR5 are known and prepared as described in WO 99/03894(compounds 102 and 101)

PR3 is prepared from tetraethylisoindolin-N-oxyl described in EP-A-135280, which is reacted with ethyl-benzene and di-tert-butylperoxide inthe presence of UV light as described in GB 2 335 190, example 6. Acolorless oil is obtained. Chemical analysis calculated: C, 82.24%; H,9.20%; N, 4.00%; found: C, 82.12%; H, 9.49%; N, 4.00%.

PR4 is prepared from tetraethylisoindolin-N-oxyl described in EP-A-135280, which is reacted with azo-bis-cyclohexane-carbonitril in analogy toexample 14 as described in GB 2 335 190. Colorless crystals are obtainedwith a melting point of 122-125° C. Chemical analysis calculated: C,77.92%; H, 9.67%; N, 7.90%; found: C, 77.81%; H, 9.67%; N, 7.82%.

PR6 is prepared fromN-t-butyl-1-diethylphosphono-2,2-dimethylpropylamin-1-oxyl described inWO 96/24620, which is reacted with ethyl-benzene anddi-tert-butylperoxide in the presence of UV light as described in GB 2335 190, example 6. A colorless oil is obtained.

1H-NMR(selected lines in CDCL₃: 5.00 ppm (1H, quartet, Ph—CH—).

1. Homopolymerizations With(4-Acryloyloxy-1,2,2,6,6-pentamethylriperidine (APP)

A1) Poly(4-acryloyloxy 1,2,2,6,6-Pentamethylpiperidine)

A tared 50 ml round-bottom flask, equipped with magnetic stirrer andreflux condenser, is charged with 0.846 g (2.6 mmol) of PR 1, 10 g (44.4mmol) of 4-acryloyloxy-1,2,2,6,6-pentamethylpiperidine (APP) and 5 g ofn-pctane. This solution is cooled using dry ice/acetone and is evacuatedunder high vacuum. The solution is then rinsed with argon and the sameprocess is repeated twice. The reaction solution is stirred for 5 hoursat 130° C. under argon. Subsequently, the reaction solution is cooled toroom temperature and the solvent as well as the unreacted monomer areremoved by evaporation at a maximum of 80° C. under water-jet vacuum andthen under high vacuum.

Yield: 4.6 g (46%); GPC: Mn=1000 Mw=1400 PD=1.4.

A2) Poly(4-acryloyloxy-1,2,2,6,6-pentamethytpiperidine)

The procedure of Example A1) is repeated, but replacing PR 1 with 0.814g (2.3 mmol) of PR 3 and reacting it with 8.7 g (38.6 mmol) of APPmonomer and.4.4 g of n-octane.

Yield: 8.4 g (97%); GPC: Mn=900 Mw=1100 PD=1.3.

A3) to A6) Poly(4-acryloyloxy-1,2,2,6,6-pentamethylpiperidine) preparedwith 6 mol % polymerization regulators (PR);

Ex. No. PR Yield Mn Mw PD A3 PR 4 50% 800 900 1.1 A4 PR 2 99% 1700 28001.6 A5 PR 5 96% 1900 2800 1.5 A6 PR 6 93% 1600 2500 1.5

2. UV Absorber Homopolymers

A7) Poly(4-acryloyloxy-2-hydroxybenzophenone)

In a 50 ml round-bottom flask, equipped with magnetic stirrer and refluxcondenser, 10 g (37.3 mmol) of 4-acryloyloxy-2-hydroxybenzophenone arepolymerized with 5 ml of dioxan and 0.8049g (2.2 mmol) of PR 2 for 5hours at 10° C. The solution is precipitated in acetonitrile, giving 8.3g (75%) of a yellowish solid.

GPC: Mn=3900 Mw=7000 PD=1.8.

A8) Poly(2-methylacrylicAcid-6-(3-benzotriazol-2-yl-5-tert-butyl-4-hydroxyphenyl)hexyl Ester

In a 50 ml round-bottom flask, equipped with magnetic stirrer and refluxcondenser, 10 g (22.9 mmol) of 2-methylacrylicacid-6-(3-benzotriazol-2-yl-5-tert-butyl-4-hydroxyphenyl)hexyl ester arepolymerized with 5 ml of dioxan and 0.495 g (1.4 mmol) of PR 2 for 5hours at 105° C. The solution is precipitated in n-hexane, giving 8.6 g(81%) of a yellowish solid.

GPC: Mn=4700 Mw=7100 PD=1.5.

3. Copolymers

A9) Random Copolymer of n-Butylacrylate and APP

1.57 g (4.4 mmol) of PR 2, 7 g (54.6 mmol) of n-butylacrylate, 12.3 g(54.6 mmol) of APP and 9.7 g of octane are polymerized in a 100 mlround-bottom flask for 5 hours at 130° C. The solvent and the unreactedmonomer are removed by evaporation under high vacuum.

Yield: 20.6 g (99%) of a viscous liquid. GPC: Mn=3300 Mw=6900 PD=2.1.

A10) Random Copolymer of n-Butylacrylate andMethacryloyloxy-1,2,2,6,6,-pentamethylpiperidine (MAPP)

1.57 g (4.4. mmol) of PR 2, 7 g (54.6 mmol) of n-butylacrylate, 13.1 g.(54.6 mmol) of APP and 10 g of octane are polymerized in a 100 mlround-bottom flask for 5 hours at 130° C. The solvent and the unreactedmonomer are removed by evaporation under high vacuum.

Yield: 21.4 g (99%) of a clear viscous liquid. GPC: Mn=3800 Mw=8600PD=2.3.

A11) Random Copolymer of Styrene and MAPP

1.67 g (4.6 mmol) of PR 2, 6.0 g (58.1 mmol) of styrene, 13.9 g (58.1mmol) of MAPP and 10 g of octane are weighed into a 100 ml round-bottomflask. The degassed solution is polymerized for 5 hours at 130° C. andthe volatile components are separated off, giving 19.8 g (91%) ofoligomer.

GPC: Mn=1300 Mw=1900 PD=1.4.

4. Block Copolymers

A 12) Block Copolymer of APP and 2-Hydroxyethylacrylate

A 100 ml round-bottom flask is charged with 1.44 g (4 mmol) of PR 2, 15g (66 mmol) of APP and 7.5 g of octane, and this mixture is polymerizedfor 2.5 hours at 130° C. All volatile components are then removed undervacuum. Yield: 16.2 g (99%). 3.9 g (33 mmol) of 2-hydroxyethylacrylateand 9.5 g of octane are added to this polymer, and this mixture isdegassed and polymerized for another 2.5 hours at 130° C. Again, allvolatile components are removed under vacuum.

Yield: 20 g (98%); Total yield over both polymerization pocesses: 97%.GPC: Mn=1400 Mw=2100 PD=1.6.

A13) to A16) Block Copolymers:

In analogy to Example A12), the following 4 block copolymers areprepared from equivalent amounts of monomers and 4 mol % of PR 2:

Example Monomer 1 Monomer 2 Yield Mn Mw PD A13 N-butylacrylate MAPP 94%2000 3800 1.9 A14 styrene APP 45% 1200 1600 1.4 A15 n-butylacrylate APP92% 1400 2100 1.6 A16 APP methylmeth- 57% 1200 4300 3.5 acrylate

B) Polymerization Examples Using Compounds of Formula (III)

and an Oxidizable Transition Metal Complex Catalyst

In polymerization's B1) and B2), 6 mol % (based on the monomer) of2-bromo-methylpropionate (Fluka, purum), 3 mol % Cu(I)Br (Fluka, purum)and 3 mol % N,N,N′,N″,N″-pentamethyl-diethylentriamine (PMDETA, Fluka,purum) is used.

Homopolymerizations:

B1) Synthesis ofPoly(4-methacryloyloxy-1,2,2,6,6-pentamethylpiperidine).

A 100 ml round bottom flask, equipped with magnetic stirrer, refluxcondenser and septum is charged with 0.360 g (2.51 mmol) CuBr, 20.0 g(83.56 mmol) 4-methacryloyloxy-1,2,2,6,6-pentamethylpiperidine and 10 gn-octane. While stirring, the mixture is degassed in vacuo and purgedwith nitrogen 3 times. 0.43 g (2.51 mmol) of the ligand PMDETA issubsequently added via syringe and the mixture heated to 50° C. (oilbath). 0.837 g (5.02 mmol) 2-bromo-methylpropionate (initiator) issubsequently added via syringe and the temperature raised to 80° C. Theexothermic polymerization reaction starts and by cooling with ice thetemperature is controlled not to exceed 100° C. After 6 h polymerizationtime, the, conversion (determined by ¹H-NMR in CDCl₃) is almostquantitative. The reaction mixture is cooled to R.T. diluted with 20 mlethylacetate, 20 g aluminumoxide(Merck) added, 1 h stirred at R.T andfiltered (to adsorb the catalyst). The solvents are subsequentlyevaporated in a rotary evaporator and the polymer dried in high vacuumat 60° C. over night.

Yield: 19.0 g (95%); GPC (THF): M_(n)=4100, M_(w)=5330, PDI=1.30. (calc:M_(n)=3990.).

B2) Synthesis ofPoly(4,6-bis(2,4-dimethylphenyl)-2(2-hydroxy-acryloxyphenyl)-triazine).

A 100 ml round bottom flask, equipped with magnetic stirrer, refluxcondenser and septum is charged with 0.191 g (1.33 mmol) CuBr, 20.0 g(44.3 mmol)4,6-bis(2,4-dimethylphenyl)-2(2-hydroxy-acryloxyphenyl)-triazine and 10g n-octane. While stirring, the mixture is degassed in vacuo and purgedwith nitrogen 3 times. 0.23 g (1.33 mmol) of the ligand PMDETA issubsequently added via syringe and the mixture heated to 50° C. (oilbath). 0.444 g (2.66 mmol) 2-bromo-methylpropionate (initiator) issubsequently added via syringe and the temperature raised to 80° C. Theexothermic polymerization reaction starts and the temperature reachesalmost 100° C. After 6 h polymerization time, the conversion (determinedby ¹H-NMR in CDCl₃) is almost quantitative. The reaction mixture iscooled to R.T., diluted with 20 ml ethylacetate, 20 galuminumoxide(Merck) added, 1 h stirred at R.T and filtered (to adsorbthe catalyst). The solvents are subsequently evaporated in a rotaryevaporator and the polymer dried in high vacuum at 60° C. over night.

Yield: 19.3 g (97%). GPC (THF): M_(n)=7400, M_(w)=9300, PDI=1.26. (calc:M_(n)=7520.)

B3 ATRP Polymerization of a Benztriazole UV-absorber Methacrylate

Into a 250 ml 3-necked flask 0.253 g (2.55 mmol) Cu(I)Cl (Fluka purum)and 40.0 g (0.0851 mol) of the monomer were added and the reactionvessel evacuated and purged with N₂ 3 times. 40 ml acetone (Fluka purum)was added, the mixture homogenized by magnetic stirring and againevacuated and purged with N₂ 3 times. 0.442 g (2.55 mmol) of the ligandpentamethyl-diethylene-triamine (PMDETA, Fluka purum) was added with asyringe via a septum followed by 1.661 g (8.51 mmol) of the initiator,ethyl-α-bromo-isobutyrate (Fluka purum). The homogeneous mixture washeated to 60° C. during 2.5 h. Conversion (¹H-NMR): ca. 100%. Aftercooling, the mixture was diluted with 50 ml ethylacetate, stirred with2×40 g Al₂O₃ and each time filtered (to remove the catalyst). Thesolvents were evaporated and the macromonomer dried at 100° C. in highvacuum (p<0.1 mbar).

Yield: 34.6 g (83%) slightly yellow powder. Analysis: GPC (THF,PS-standards): M_(n)=6990, M_(w)=8280, PDI=1.18 (M_(n) (calc.)=4890);EI.-analysis: calc C, 64.04; H, 6.50; N, 8.42; Br, 0.80; found C, 63.70;H, 6.31; N, 8.08; Br, 0.70.

B4 ATRP Polymerization of a Benztriazole UV-absorber Methacrylate(NORBLOC 7966)

Into a 350 ml 3-necked flask 0.408 g (4.13 mmol) Cu(I)Cl (Fluka purum)and 45.0 g (0.137 mol) of the monomer NORBLOC 7966 were added and thereaction vessel evacuated and purged with N₂ 3 times. 125 ml acetone(Fluka purum) was added, the mixture homogenized by magnetic stirringand again evacuated and purged with N₂ 3 times. 0.715 g (4.13 mmol) ofthe ligand pentamethyl-diethylene-triamine (PMDETA, Fluka purum) wasadded with a syringe via a septum followed by 2.684 g (13.7 mmol) of theinitiator, ethyl-α-bromo-isobutyrate (Fluka purum). The homogeneousmixture was heated to 60° C. during 17 h. Conversion (¹H-NMR): ca. 100%.After cooling, the mixture was diluted with 200 ml dioxane, stirred with50 g Al₂O₃ for 30 min. and filtered (to remove the catalyst). Thepolymer was precipitated 3× in 300 ml MeOH, filtered and dried at 40° C.in high vacuum (p<0.1 mbar) for 24 h.

Yield: 39.15 g (82%) yellow powder. Analysis: GPC (THF, PS-standards):M_(n)=4610, M_(w)=5740, PDI=1.24 (M_(n) (calc.)=3470); EI.-analysis:calc C, 67.39; H, 6.16; N, 12.77; Br, 1.21; found C, 67.40; H, 5.38; N,12.20; Br, 0.35.

B5 ATRP Copolymerization of a Benztriazole UV-absorber Methacrylate(NORBLOC 7966) With Methyl-methacrylate (MMA)

Into a 250 ml 3-necked flask with mechanical stirring 0.215 g (2.18mmol) Cu(I)Cl (Fluka purum) and 35.0 g (72.6 mmol) of the first monomer(benzotriazol) were added and the reaction vessel evacuated and purgedwith N₂ 3 times. 50 ml acetone (Fluka purum) and 7.277 g (72.6 mmol)methyl-methacrylate (MMA, Fluka purum) were added, the mixturehomogenized by mechanical stirring and again evacuated and purged withN₂ 3 times. 0.377 g (2.18 mmol) of the ligandpentamethyl-diethylene-triamine (PMDETA, Fluka purum) was added with asyringe via a septum followed by 1.417 g (7.26 mmol) of the initiator,ethyl-α-bromo-isobutyrate (Fluka purum). The homogeneous mixture washeated to 60° C. during 6 h. Conversion (¹H-NMR): ca. 100%. Aftercooling, the mixture was diluted with 60 ml dioxane, stirred with 50 gAl₂O₃ for 30 min. and filtered (to remove the catalyst). The polymer wasprecipitated in 800 ml MeOH/H₂O (1:5) filtered and dried at 40° C. inhigh vacuum (p<0.1 mbar) for 24 h.

Yield: 35.75 g (81.4%) slightly yellow powder. Analysis: GPC (THF,PS-standards): M_(n)=7430, M_(w)=9930, PDI=1.34 (M_(n) (calc.)=6010);EI.-analysis: calc C, 63.37; H, 6.75; N, 7.02. found C, 62.43; H, 6.74;N, 6.75.

C) Application Results

Impact Strength as a Function of Artificial Weathering

Commercially available PE or PP (Hostalen® GM 6255, supplier: Hoechst,MFR_((260/21.6))=4.55, stabilizer residues: 420 ppm Irganox 1010+1400ppm Irgafos 168; Profax® 6501, supplier: Montell, MFR_((230/2.16))=566,stabilizer residues: 45 ppm Irganox 1076) is extruded together with thecompounds given in Table 1 on a twin screw extruder (TW 100, Haake) at225-240° C. (heating zones 1-5) and 30 rpm.

The granulated polymer is injection molded at 240° C. (A 221-75-350,Arburg) to test samples. The tensile impact strength of these testsamples is determined as a function of artificial weathering.

The weatherings are carried out in a Weather-O-Meter (Cl 65A, Atlas;black. panel temperature=63° C., relative humidity=60%, water spray).The compositions and test results are shown in Table 2 and 3. The higherthe impact strength value, the more stable the tested composition

TABLE 2 Artificial weathering of PE Tensile impact strength [kJ/m2]Example Additives 0 h 500 h 1000 h 1500 h 2000 h 3000 h C1 without 835143  52  49  41  41 C2 0.2% Tinuvin 326 880 941 902 510 461 394 C3 0.2%Chimassorb 946 948 688 529 435  52 944 C4 0.2% polymer of 884 896 847716 667 547 example A5 C5 0.2% polymer of 989 950 1016  893 958 792example A8

TABLE 3 Artificial weathering of PP Tensile impact strength [kJ/m2]Example Additives 0 h 500 h 1000 h 1500 h 2000 h 3000 h C6 0.2% IrganoxB225 458  41  41  41  41  41 0.05% Ca-stearate C7 0.2% Irganox B225 458487 436 195  82  44 0.05% Ca-stearate 0.2% Tinuvin 622 C8 0.2% IrganoxB225 479 536 281 208 173 140 0.05% Ca-stearate 0.2% Tinuvin 326 C9 0.2%Irganox B225 435 465 385 376 309  94 0.05% Ca-stearate 0.2% Chimassorb944 C10 0.2% Irganox B225 448 440 431 369 327 205 0.05% Ca-stearate 0.4%polymer of example A15* *block copolymer with equal block lengths (0.4%additive ≈ 0.2% stabilizer content)

The values obtained show that the samples containing the oligomericcompounds stabilize the polymer more effectively when aged over aprolonged period of time than the samples containing the conventionalstabilizers.

What is claimed is:
 1. A polymerizable composition, comprising a) atleast one compound of formula (I) (RG)—A—(Stab)  (I)  wherein (Stab) isa light stabilizer radical selected from the group consisting ofsterically hindered amines, hydroxyphenyl-s-triazines,hydroxyphenyl-benzotriazols and o-hydroxy-benzophenones; A is a spacergroup or a direct bond; and (RG) is a group containing at least oneethylenically unsaturated functional group; and a compound selected fromthe group consisting of b1) a compound of formula (II) Y—X  (II)  whichcontains a structural element>N—O—X where the nitrogen atom is part of acyclic ring system or is substituted to form an acyclic structure, andwherein X represents a group having at least one carbon atom and is suchthat the free radical derived from X is capable of initiatingpolymerization; and a compound selected from the group consisting of b2)a stable free radical having a structural element>N—O· where thenitrogen atom is part of a cyclic ring system or is substituted to forman acyclic structure and a free radical source from which a radical isformed capable of initiating polymerization; b3) a compound of formula(III)

 and a catalytically effective amount of an oxidizable transition metalcomplex catalyst where the transition metal is present as a transitionmetal complex ion in the lower oxidation state of a redox system; wherein [In] represents a polymerization initiator fragment of apolymerization initiator of formula (III) capable of initiatingpolymerization of monomers or oligomers, which polymerization initiatoris selected from the group consisting of C₁-C₈-alkyl halides,C₆-C₁₅-aralkylhalides, C₂-C₈α-haloalkyl esters, arene sulfonylchlorides, haloalkanenitriles, α-haloacrylates and halolactones; p and qrepresent one; and -[Hal] represents a leaving group; and optionally c)one or more ethylenically unsaturated monomers or oligomers differentfrom those of formula (I).
 2. A composition according to claim 1,wherein the compound of formula (I) is a compound of formulae (Ia),(Ib), (Ic), (Id), (Ie), (If), (Ig), (Ih), (Ii) or (Ij)

W is O or NR₁₁₀; A is a direct bond, —(C₂-C₁₂)alkylene-W—,—(C₃-C₁₂)alkenylene-W—, —CH₂—HC(OH)—CH₂—W—, —(C₃-C₁₂)alkinylene-W—,(C₅-C₁₂)cycloalkylene-W—, —(C₂-C₁₂)alkylene-W— interrupted by at leastone oxygen or nitrogen atom or a group —CH₂—CHR₁₁₀—W—, a group—CHR₁₁₁—COOP wherein P is —(CH₂—HC₁₁₂)_(n)— or a group —CH₂—HC(OH)—CH₂—,wherein R₁₀₀, R₁₁₁, R₁₁₂ and n are as defined below; R₁₀₁ is H or methylR₁₀₂ is hydrogen, OH, C₁-C₁₈alkyl, C₃-C₈alkenyl, C₃-C₈alkynyl,C₇-C₁₂aralkyl, C₁-C₁₈alkanoyl, C₃-C₁₈alkenoyl, C₁-C₁₈alkanoyloxy,glycidyl, C₁-C₁₈alkoxy, C₅-C₁₂cycloalkyl, C₅-C₁₂cycloalkoxy or a group—CH₂CHR₁₁₀(OH); R₁₀₃ is H, OH, NH₂, C₁-C₁₈alkoxy, C₁-C₁₈alkanoyloxy,C₆-C₁₈aryloyloxy, C₁-C₁₈alkanoylamino, C₁-C₁₈alkylamino,C₁-C₁₈dialkylamino, benzyloxy or together with the linking carbon atomforms a C₅-C₆cycloalkyl radical or a C₅-C₆heterocycloalkyl radicalcontaining one or two oxygen or nitrogen atoms; R₁₀₄, R₁₀₅, R₁₀₆, R₁₀₇are independently C₁-C₈alkyl or C₅-C₁₂cycloalkyl, or R₁₀₄ and R₁₀₅and/or R₁₀₆ and R₁₀₇ together with the carbon atom to which they areattached form a C₅-C₁₂cycloalkyl group; R₁₀₈ and R₁₀₉ independently areH, C₁-C₈alkyl or phenyl; R₁₁₀ is hydrogen, C₁-C₁₈alkyl or phenyl; R₁₁₁is hydrogen or C₁-C₁₂alky; R₁₁₂ is hydrogen or methyl; R₂₀₁ and R₂₀₂ areindependently H, OH, CN, C₁-C₁₈alkyl, C₁-C₁₈alkoxy, halogen,C₁-C₁₈alkanoyl, C₁-C₁₈alkanoyloxy, C₁-C₁₈alkanoylamino, or phenyl whichis unsubstituted or substituted with halogen, OH, CN, NO₂, C₁-C₁₈alkyl,C₁-C₁₈alkoxy or a group —O—CH₂—HC(OH)—CH₂—OR₂₀₆; R₂₀₃ and R₂₀₄ areindependently H, OH, CN, C₁-C₁₈alkyl, C₁-C₁₈alkoxy, halogen,C₁-C₁₈alkanoyl, C₁-C₁₈alkanoyloxy, C₁-C₁₈alkanoylamino, or phenyl whichis unsubstituted or substituted with halogen, OH, CN, NO₂, C₁-C₁₈alkyl,C₁-C₁₈alkoxy or a group —O—CH₂—HC(OH)—CH₂—OR₂₀₆ with the proviso that atleast one of both is OH; R₂₀₅ is H, halogen, phenyl, C₁-C₁₈alkyl,C₅-C₁₂cycloalkyl, C₇-C₁₂aralkyl or a group —SR₂₀₈, —SO₂R₂₀₈, —COOR₂₀₈ orPO(OR₂₀₈)₂; R₂₀₆ is C₁-C₁₈alkyl, C₃-C₁₈alkyl interrupted by at least oneoxygen atom, phenyl which is unsubstituted or substituted with halogen,OH, CN, NO₂, C₁-C₁₈alkyl, C₁-C₁₈alkoxy, C₅-C₆cycloalkyl which isunsubstituted or substitueted by C₁-C₄alkyl or a group —C(O)R₂₀₇; R₂₀₇C₁-C₁₈alkyl or phenyl which is unsubstituted or substituted withhalogen, OH, CN, NO₂, C₁-C₁₈alkyl or C₁-C₁₈alkoxy; R₂₀₈ is C₁-C₁₈alkyl,C₅-C₆cycloalkyl or phenyl; R₂₀₉ is H, halogen, phenyl, C₁-C₁₈alkyl,C₅-C₁₂cycloalkyl, C₇-C₁₂aralkyl or a group —SR₂₀₈, —SO₂R₂₀₈, —COOR₂₀₈ orPO(OR₂₀₈)₂; n is a number from 0 to 12; and k is a number from 0 to 12.3. A composition according to claim 2, wherein R₁₀₈ and R₁₀₉ arehydrogen and the other substituents are as defined in claim
 2. 4. Acomposition according to claim 2, wherein in the compounds of formulae(Ia), (Ib), (Ic), (Id) and (Ie) R₁₀₄, R₁₀₅, R₁₀₆ and R₁₀₇ are methyl andthe other substituents are as defined in claim
 2. 5. A compositionaccording to claim 2, wherein A is a direct bond, —(C₂-C₆)alkylene-W—,—(C₂-C₁₂)alkylene-W— interrupted by at least one oxygen or nitrogen atomor a group —CH₂—CHCH₃—W—.
 6. A composition according to claim 2, whereinR₁₀₂ is hydrogen, C₁-C₈alkyl, allyl, benzyl, C₁-C₈alkanoyl,C₁-C₈alkanoyloxy, C₁-C₈alkoxy or cyclohexyloxy.
 7. A compositionaccording to claim 2, wherein the compound of formula (I) is a compoundof formulae (Ia), (Ic), (Id), (If), (Ig), (Ii) or I(j).
 8. A compositionaccording to claim 1, wherein in the compound of formula (Ia), A is adirect bond; W is an oxygen atom; RG is a group

R₁₀₁ is H or methyl; R₁₀₂ is H or C₁-C₄alkyl; R₁₀₄-R₁₀₇ are methyl; andR₁₀₈ and R₁₀₉ are hydrogen.
 9. A composition according to claim 1,wherein in the compound of formula (Ii) A is a direct bond W is anoxygen atom; RG is a group

R₁₀₁ is H or methyl; R₂₀₅ is H C₁-C₈alkyl, phenyl or α-cumyl; R₂₀₉ is Hor Cl and k is a number from 1 to
 8. 10. A composition according toclaim 1, wherein the ethylenically unsaturated monomer or oligomer c) isselected from the group consisting of alkene, styrene, substitutedstyrene, conjugated dienes, acrolein, vinyl acetate, (alkyl)acrylicacidanhydrides, (alkyl)acrylic acid salts, (alkyl)acrylic esters or(alkyl)acrylamides.
 11. A composition according to claim 10, wherein theethylenically unsaturated monomer is styrene, methylacrylate,ethylacrylate, butylacrylate, isobutylacrylate, tert. butylacrylate,hydroxyethylacrylate, hydroxypropylacrylate, dimethylaminoethylacrylate,glycidylacrylates, methyl(meth)acrylate, ethyl(meth)acrylate,butyl(meth)acrylate, hydroxyethyl(meth)acrylate,hydroxypropyl(meth)acrylate, dimrethylaminoethyl(meth)acrylate,glycidyl(meth)acrylates, acrylonitrile, acrylamide or methacrylamide.12. A composition according to claim 1 wherein the structural element

is a 1-alkoxy-polyalkyl-piperidine derivative containing a structuralelement of formula (X)

G₁, G₂, G₃, G₄ are independently C₁-C₆alkyl with the proviso that atleast one is not methyl or G₁ and G₂ or G₃ and G₄, or G₁ and G₂ and G₃and G₄ together form a C₅-C₁₂cycloalkyl group; G₅, G₆ independently areH, C₁-C₁₈alkyl, phenyl, naphthyl or a group COOC₁-C₁₈alkyl and Xrepresents a group having at least one carbon atom and is such that thefree radical X· derived from X is capable of initiating polymerizationof ethylenically unsaturated monomers.
 13. A composition according toclaim 1, wherein the compound containing a structural element

is of formula (Xa) or (Xb)

R₁, R₂, R₃ and R₄ independently of each other are C₁-C₁₈alkyl,C₃-C₁₈alkenyl, C₃-C₁₈alkinyl, C₁-C₁₈alkyl, C₃-C₁₈alkenyl, C₃-C₁₈alkinylwhich are substituted by OH, halogen or a group —O—C(O)—R₅, C₂-C₁₈alkylwhich is interrupted by at least one O atom and/or NR₅ group,C₃-C₁₂cycloalkyl or C₆-C₁₀aryl or R₁ and R₂ and/or R₃ and R₄ togetherwith the linking carbon atom form a C₃-C₁₂cycloalkyl radical; R₅, R₆ andR₇ independently are hydrogen, C₁-C₁₈alkyl or C₆-C₁₀aryl; X represents agroup having at least one carbon atom and is such that the free radicalX· derived from X is capable of initiating polymerization ofethylenically unsaturated monomers; Z₁ is O or NR₈; R₈ is hydrogen, OH,C₁-C₁₈alkyl, C₃-C₁₈alkenyl, C₃-C₁₈alkinyl, C₁-C₁₈alkyl, C₃-C₁₈alkenyl,C₃-C₁₈alkinyl which are substituted by one or more OH, halogen or agroup —O—C(O)—R₅, C₂-C₁₈alkyl which is interrupted by at least one Oatom and/or NR₅ group, C₃-C₁₂cycloalkyl or C₆-C₁₀aryl, C₇-C₉phenylalkyl,C₅-C₁₀heteroaryl, —C(O)—C₁-C₁₈alkyl, —O—C₁-C₁₈alkyl or —COOC₁-C₁₈alkyl;Q is a direct bond or a divalent radical CR₉R₁₀, CR₉R₁₀—CR₁₁R₁₂,CR₉R₁₀CR₁₁R₁₂CR₁₃R₁₄, C(O) or CR₉R₁₀C(O), wherein R₉, R₁₀, R₁₁, R₁₂, R₁₃and R₁₄ are independently hydrogen, phenyl or C₁-C₁₈alkyl.
 14. Acomposition according to claim 1, wherein X is selected from the groupconsisting of —CH₂-aryl,

(CH₃)₂C-aryl, (C₅-C₆cycloalkyl)₂CCN, (C₁-C₁₂alkyl)₂CCN, —CH₂CH═CH₂,(C₁-C₁₂)alkyl-CR₂₀—C(O)—(C₁-C₁₂alkyl,(C₁-C₁₂)alkyl-CR₂₀—C(O)—(C₆-CIO)aryl,(C₁-C₁₂)alkyl-CR₂₀—C(O)—(C₁-C₁₂)alkoxy, (C₁-C₁₂)alkyl-CR₂₀—C(O)-phenoxy,(C₁-C₁₂)alkyl-CR₂₀—C(O)—N-di(C₁-C₁₂)alkyl,(C₁-C₁₂)alkyl-CR₂₀—CO—NH(C₁-C₁₂)alkyl, (C₁-C₁₂)alkyl-CR₂₀—CO—NH₂,—CH₂CH═CH—CH₃, —CH₂—C(CH₃)═CH₂, —CH₂—CH═CH-phenyl,

 wherein R₂₀ is hydrogen or C₁-C₁₂alkyl, the aryl groups areunsubstituted or substituted with C₁-C₁₂alkyl, halogen, C₁-C₁₂alkoxy,C₁-C₁₂alkylcarbonyl, glycidyloxy, OH, —COOH or —COOC₁-C₁₂alkyl.
 15. Acomposition according to claim 14, wherein X is selected from the groupconsisting of —CH₂-phenyl, —CH₃CH-phenyl, (CH₃)₂C-phenyl,(C₅-C₆cycloalkyl)₂CCN, (CH₃)₂CCN, —CH₂CH═CH₂, CH₃CH—CH═CH₂,(C₁-C₄alkyl)CR₂₀—C(O)-phenyl, (C₁-C₄)alkyl-CR₂₀—C(O)—(C₁-C₄)alkoxy,(C₁-C₄)alkyl-CR₂₀—C(O)—(C₁-C₄)alkyl,(C₁-C₄)alkyl-CR₂₀—C(O)—N-di(C₁-C₄)alkyl,(C₁-C₄)alkyl-CR₂₀—C(O)—NH(C₁-C₄)alkyl, (C₁-C₄)alkyl-CR₂₀—C(O)—NH₂,wherein R₂₀ is hydrogen or (C₁-C₄)alkyl.
 16. A composition according toclaim 1, wherein the transition metal complex ion is a Cu(I) complex ionin the Cu(I)/Cu(II) system.
 17. A process for preparing an oligomer,cooligomer, polymer or copolymer with a polydispersity M_(w)/M_(n)between 1 and 3, which process comprises reacting a composition of a) atleast one compound of formula (I) (RG)—A—(Stab)  (I)  wherein (Stab) isa light stabilizer radical selected from the group consisting ofsterically hindered amines, hydroxyphenyl-s-triazines,hydroxyphenyl-benzotriazols and o-hydroxy-benzophenones; A is a spacergroup or a direct bond; and (RG) is a group containing at least oneethylenically unsaturated functional group; and a compound selected fromthe group consisting of b1) a compound of formula (II) Y—X  (II)  whichcompound contains a structural element>N—O—X where the nitrogen atom ispart of a cyclic ring system or is substituted to form an acyclicstructure, and wherein X represents a group having at least one carbonatom and is such that the free radical derived from X is capable ofinitiating polymerization; b2) a stable free radical having a structuralelement>N—O· where the nitrogen atom is part of a cyclic ring system oris substituted to form an acyclic structure and a free radical sourcefrom which a radical is formed capable of initiating polymerization; b3)a compound of formula (III)

a catalytically effective amount of an oxidizable transition metalcomplex catalyst, where the transition metal is present as a transitionmetal complex ion in the lower oxidation state of a redox system; wherein [In] represents a polymerization initiator fragment of apolymerization initiator of formula (III) capable of initiatingpolymerization of monomers or oligomers, which polymerization initiatoris selected from the group consisting of C₁-C₈-alkyl halides,C₆-C₁₅-aralkylhalides, C₂-C₈α-haloalkyl esters, arene sulfonylchlorides, haloalkanenitriles, α-haloacrylates and halolactones; p and qrepresent one; and -[Hal] represents a leaving group; and optionallysimultaneously or in a subsequent step with c) one or more ethylenicallyunsaturated monomers or oligomers different from those of formula (I),at a temperature between 50° C. and 180° C.
 18. A process according toclaim 17, wherein the molecular weight M_(n) of the polymer copolymer,oligomer or cooligomer is between 1000 and 100
 000. 19. A processaccording to claim 17, wherein the polydispersity is from 1.0 to
 2. 20.A oligomer, polymer, cooligomer or copolymer obtained according to theprocess of claim
 17. 21. An organic material stabilized against heat,actinic or electromagnetic radiation ranging from γ to infrared with aoligomer, polymer, cooligomer or copolymer obtained according to theprocess of claim 17.